Substituted quinolines and cinnolines as fungicides

ABSTRACT

A fungicidal method which comprises applying to the locus of a plant pathogen a fungicidally effective but non-phytotoxic amount of a compound of the formula (1) ##STR1## wherein: R 1  to R 4  are independently 
     H, halo, (C 1  -C 4 ) alkyl, branched (C 3  -C 4 ) alkyl, halo (C 1  -C 4 ) alkyl, (C 1  -C 4 ) alkoxy, NO 2 , or HN 2 , at least two of R 1  to R 4  being H, 
     or one of R 2  to R 4  is --NR 7  --Y--Ar or O--Y--Ar and the rest of R 1  to R 4  are H; 
     W is N, or CR 5  ; 
     R 5  is H, CH 3 , Cl, O--Y--Ar, or --NR 7  --Y--Ar; 
     R 6  is H, CH 3 , Cl, or Br; 
     A is --O--Alk or --X--Y--Ar; 
     Alk is a C 2  -C 18  saturated or unsaturated hydrocarbon chain, straight chain or branched, optionally substituted with halo, halo (C 1  -C 4 ) alkoxy, (C 3  -C 8 ) cycloalkyl, hydroxy, or acetyl; 
     X is O, NR 7 , or CR 8  R 9 , provided that if one of R 2  to R 5  is NR 7  --Y--Ar or O--Y--Ar, then X--Y--Ar is an identical group; 
     R 7  is H, (C 1  -C 4 ) alkyl, or acetyl; 
     R 8  and R 9  are independently H, (C 1  -C 4 ) alkyl, halo, or OH, or R 8  and R 9  combine to form a saturated or unsaturated carbocyclic ring comprising three to seven carbon atoms; 
     Y is an alkylene chain 2 to 8 carbon atoms long that optionally includes an O, S, SO, SO 2 , or NR 7  group, and optionally includes a saturated or unsaturated carbocyclic ring comprising three to seven carbon atoms, and optionally is substituted with (C 1  -C 3 ) alkyl, (C 1  -C 4 ) alkenyl, phenyl, (C 3  -C 8 ) cycloalkyl, hydroxy, halo, or acetyl; and 
     Ar is an aryl group.

RELATED APPLICATIONS

This application is a continuation-in-part of U.S. Appln. Ser. No.07/150,366, filed Jan. 29, 1988, now abandoned.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention provides new compounds that have excellent plantfungicide activity. Some of the compounds have also demonstratedinsecticidal and miticidal activity. The invention also providescompositions and combination products that contain a compound of theinvention as active ingredient. The invention also provides fungicidal,miticidal, and insecticidal methods.

There is an acute need for new fungicides, insecticides, and miticides,because target pathogens are rapidly developing resistance to currentlyused pesticides. Widespread failure of N-substituted azole fungicides tocontrol barley mildew was observed in 1983, and has been attributed tothe development of resistance. At least 50 species of fungi havedeveloped resistance to the benzimidazole fungicides. The fieldperformance of DMI (demethylation inhibitor) fungicides, which are nowwidely relied on to protect cereal crops from powdery mildew, hasdeclined since they were introduced in the 1970's. Even recentfungicides, like the acylalanines, which initially exhibited excellentcontrol of potato late blight and grape downy mildew in the field, havebecome less effective because of widespread resistance. Similarly, mitesand insects are developing resistance to the miticides and insecticidesin current use. Resistance to insecticides in arthropods is widespread,with at least 400 species resistant to one or more insecticides. Thedevelopment of resistance to some of the older insecticides, such asDDT, the carbamates, and the organophosphates, is well known. Butresistance has even developed to some of the newer pyrethroidinsecticides and miticides. Therefore a need exists for new fungicides,insecticides, and miticides.

SUMMARY OF THE INVENTION

This invention provides compounds of the formula (1): ##STR2## wherein:R¹ to R⁴ are independently

H, halo, (C₁ -C₄) alkyl, branched (C₃ -C₄) alkyl, halo (C₁ -C₄) alkyl,(C₁ -C₄) alkoxy, NO₂, or NH₂, at least two of R¹ to R⁴ being H,

or one of R² to R⁴ is --NR⁷ --Y--Ar or O--Y--Ar and the rest of R¹ to R⁴are H;

W is N, or CR⁵ ;

R⁵ is H, CH₃, Cl, O--Y--Ar, or --NR⁷ --Y--Ar;

R⁶ is H, CH₃, Cl or Br;

A is --O--Alk or --X--Y--Ar;

Alk is a C₂ -C₁₈ saturated or unsaturated hydrocarbon chain, straightchain or branched, Optionally substituted with halo, halo (C₁ -C₄)alkoxy, (C₃ -C₈) cycloalkyl, hydroxy, or acetyl;

X is O, NR⁷, or CR⁸ R⁹, provided that if one of R² to R⁵ is NR⁷ --Y--Aror O--Y--Ar,--then X--Y--Ar is an identiR;

R⁷ is H, (C₁ -C₄) alkyl, or acetyl;

R⁸ and R⁹ are independently H, (C₁ -C₄) alkyl, (C₁ -C₄) acyl, halo, orOH, or R⁸ and R⁹ combine to form a saturated or unsaturated carbocyclicring comprising three to seven carbon atoms;

Y is an alkylene chain 2 to 8 carbon atoms long, that optionallyincludes an O, S, SO, SO₂, or NR⁷ group, and optionally includes asaturated or unsaturated carbocyclic ring comprising three to sevencarbon atoms, and optionally is substituted with (C₁ -C₃) alkyl, (C₂-C₄) phenyl, (C₃ -C₈) cycloalkyl, hydroxy, halo, or (C₁ -C₄) acyl; and

Ar is

1,3-benzodioxolyl

fluorenyl,

pyridyl

substituted pyridyl,

indolyl,

furanyl,

substituted furanyl,

thienyl, optionally substituted with CH₂ or Cl,

thiazolyl,

cyclopentyl,

1-methylcyclopentyl,

cyclohexenyl (tetrahydrophenyl),

cyclohexyl (hexahydrophenyl),

naphthyl,

substituted naphthyl,

dihydronaphthyl,

tetrahydronaphthyl,

decahydronaphthyl, or

a group of the formula (2): ##STR3## where R¹⁰ to R¹⁴ are independentlyH, halo, I, (C₁ -C₁₀) branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, (C₁-C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, substituted phenoxy,phenylthio, substituted phenylthio, phenyl, substituted phenyl, NO₂,NH₂, acetoxy, OH, CN, SiR¹⁵ R¹⁶ R¹⁷, or OSiR¹⁵ R¹⁶ R¹⁷, where R¹⁵, R¹⁶,and R¹⁷ are independently (C₁ -C₄) alkyl or (C₃ -C₄) branched alkyl,phenyl, or substituted phenyl, provided that unless each of R¹⁰ to R¹⁴is F, CH₃, or H, then at least two of R¹⁰ to R¹⁴ are H;

or an acid addition salt of a compound of formula (1)

or an N-oxide of a compound of formula (1) when W is CR⁵

provided that the following compounds are excluded:

(1) N-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolinamine;

(2) N-(2-phenylethyl)-4-quinolinamine.

The final proviso excludes compounds that are known per se or that couldbe considered similar to known compounds.

The fungicidal combinations of the invention comprise at least 1% byweight of a compound of formula (1), orN-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolineamine orN-(2-phenylethyl)-4-quinolinamine, in combination with a secondfungicidal compound.

The fungicidal compositions of the invention comprise a diseaseinhibiting and phytologically acceptable amount of a compound of formula(1), or N-[4-(4-chlorophenyl)butyl]-7-chloro-4-quinolinamine, orN-(2-phenylethyl)-4-quinolinamine, in combination with aphytologically-acceptable carrier.

The fungicidal method of the invention comprises applying to the locusof a plant pathogen a disease inhibiting and phytologically acceptableamount of a compound of the formula (1), orN-[4-(4-chlorophenyl)butyl]7-chloro-4-quinolinamine, orN-(2-phenylethyl)-4-quinolinamine.

The insecticidal or miticidal combinations of the invention comprise atleast 1% by weight of a compound of formula (1) in combination with asecond insecticide or miticide.

The insecticide or miticide compositions of the invention comprise aninsect or mite inactivating amount of a compound of formula (1) incombination with a phytologically-acceptable carrier.

The insecticide and miticide methods of the invention comprise applyingto a locus of an insect or mite an insect or mite inactivating amount ofa compound of formula (1), or of a combination described above.

DETAILED DESCRIPTION OF THE INVENTION

Throughout this document, all temperatures are given in degrees Celsius,and all percentages are weight percentages unless otherwise stated.

The terms "(C₁ -C₃) alkyl", "(C₁ -C₄) alkyl", and "(C₁ -C₁₀) aIkyl",when used alone, refer to straight chain alkyl radicals.

The terms "branched (C₃ -C₄) alkyl", and "branched (C₃ -C₆) alkyl" referto all alkyl isomers containing the designated number of carbon atoms,excluding the straight chain isomers.

The terms "(C₁ -C₄) alkoxy" and "(C₁ -C₇) alkoxy" refer to straight orbranched chain alkoxy groups.

The term "halo" used alone or in combination with other terms refers toF, Cl, or Br;

The term "halo (C₁ -C₇) alkyl" refers to a (C₁ -C₇) alkyl group,straight chain or branched, substituted with one or more halo groups.

The term "substituted phenyl" used alone or in combination with otherterms, as in "substituted phenylthio" or "substituted phenylsulfonyl" ,refers to phenyl substituted with up to three groups selected from halo,I, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl,hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy,phenyl, NO₂, OH, CN, (C₁ -C₄) alkanoyloxy, or benzyloxy.

The term "substituted phenoxy" refers to phenoxy substituted with up tothree groups selected from halo, I, (C₁ -C₁₀) alkyl, branched (C₃ -C₆)alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy,halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN, (C₁ -C₄)alkanoyloxy, or benzyloxy.

The terms "substituted naphthyl", "substituted pyridyl" and "substitutedfuranyl" refer to these ring systems substituted with halo, halo (C₁-C₄) alkyl, CN, NO₂, (C₁ -C₄) alkyl, (C₃ -C₄) branched alkyl, phenyl,(C₁ -C₄) alkoxy, or halo (C₁ -C₄) alkoxy.

The term "unsaturated hydrocarbon chain" refers to a hydrocarbon chaincontaining one or two sites of unsaturation.

The term "HPLC" refers to high-performance liquid chromatography.

Compounds

While all of the compounds of the invention are useful fungicides,certain classes are preferred for reasons of greater efficacy or ease ofsynthesis, viz:

1. compounds of formula (1) where W is CR⁵ (i.e., substitutedquinolines);

2. compounds of preferred class (1) where R⁶ is H;

3. compounds of formula (1) where R⁶ is H;

4. compounds of formula (1) where at least three of R¹ to R⁴ are H;

5. compounds of preferred class (4) where R is F (i.e.,8-fluoroquinolines);

6. compounds of preferred class (4) where Rs is F (i.e.,7-fluoroquinolines);

7. compounds of preferred class (4) where Rs is Cl (i.e.,7-chloroquinolines);

8. compounds of preferred class (4) where Rz is F (i.e.,6-fluoroquinolines);

9. compounds of formula (1) where Y is an alkylene chain 2 to 4 carbonatoms long.

10. compounds of preferred class (9) where Y is --(CH₂)₂ --;

11. compounds of formula (1) where Ar is

12. compounds of formula (1) where Ar is

13. compounds of formula (1) where Ar is

14. compounds of formula (1) where Ar is cyclohexenyl;

15. compounds of formula (1) where Ar is a substituted phenyl group offormula (2);

16. compounds of preferred class (15) where at least three of R¹⁰ to R¹⁴are H;

17. compounds of preferred class (15) where four R¹⁰ to R¹⁴ are H;

18. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is Cl;

19. compounds of preferred class (18) where R¹² is Cl;

20. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is CF₃ ;

21. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ is (C₁-C₄) alkyl;

22. compounds of preferred class (21) wherein one of R¹⁰ to R¹⁴ ismethyl;

23. compounds of preferred class (22) wherein R¹² is methyl;

24. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ isbranched (C₃ -C₆) alkyl;

25. compounds of preferred class (24) wherein R¹² is t-butyl;

26. compounds of preferred class (24) wherein R¹² is i-propyl;

27. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ isphenyl or substituted phenyl;

28. compounds of preferred class (27) wherein R¹² is phenyl;

29. compounds of preferred class (17) wherein one of R¹⁰ to R¹⁴ isphenoxy or substituted phenoxy;

30. compounds of preferred class (29) wherein R¹² is phenoxy.

Compounds exhibiting particularly excellent activity against downymildew include:

8-fluoro-N-(2-phenylethyl)-4-quinolinamine;

8-fluoro-N-[2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine;

8-fluoro-N-[2-[2-(trifluoromethyl)phenyl]ethyl]-4quinolinamine;

N-[2-(4-chlorophenyl)ethyl]-6-methyl-4-quinolinamine;

8-chloro-N-(2-phenylethyl)-4-quinolinamine;

8-fluoro-N-[2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine;

8-fluoro-N-[2-(2-naphthyl)ethyl]-4-quinolinamine;

8-fluoro-N-[2-[3-(trifluoromethyl)phenyl]ethyl]-4quinolinamine;

7-chloro-N-[2-(1-cyclohexenyl)ethyl]-4-quinolinamine;

N-[2-[4-(1-methylethyl)phenyl]ethyl]-8-fluoro-4quinolinamine;

8-fluoro-N-[2-(2-thienyl)ethyl]-4-quinolinamine;

4-[2-(3-chlorophenyl)ethoxy]-8-fluoroquinoline;

8-fluoro-4-[2-(3-(trifluoromethyl)phenyl)ethoxy]quinoline;

4-[2-(4-methylphenyl)ethoxy]quinoline;

8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline; and

4-[2-[4-(t-butyl)phenyl]ethoxy]-8-fluoroquinoline;

Compounds exhibiting particularly excellent activity against rice blastinclude:

N-[2-(4-chlorophenyl)ethyl]-N-(8-fluoro-4-quinolinyl)acetamide;

N-[2-[4-(i-propyl)-phenyl]ethyl]-8-fluoro-4-quinolin

8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline;

8-fluoro-4-[2-(3-(trifluoromethyl)phenyl)ethoxy]quinoline;

8-fluoro-4-[2-(2-naphthyl)ethoxy]quinoline;

8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline; and

8-fluoro-4-[3-(4-(t-butyl)phenyl)propyl]quinoline;

Compounds exhibiting particularly excellent activity against a broadspectrum of plant pathogens include:

8-fluoro-N-[2-(3-phenoxyphenyl)ethyl]-4-quinolinamine;

N-[2-[4-(i-propyl)phenyl]ethyl]-8-fluoro-4-quinolin

N-[2-(1,1'-biphenyl)-3-ylethyl]-8-fluoro-4-quinolin

N-[2-(2,4-dichlorophenyl)ethyl]-8-fluoro-4-quinolin

8-fluoro-4-[3-(4-(t-butyl)phenyl)propyl]quinoline;

8-fluoro-4-[3-(4-(i-propyl)phenyl)propyl]quinoline;

8-fluoro-4-[2-(2-(trifluoromethyl)phenyl)ethoxy]quinoline;

4-[2-(4-chlorophenyl)ethoxy]-8-fluoroquinoline;

4-[2-(4-methylphenyl)ethoxy]quinoline;

8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline;

8-fluoro-4-(2-phenylethoxy)quinoline;

8-fluoro-4-[2-(3-methylphenyl)ethoxy]quinoline;

8-fluoro-4-[2-(2-fluorophenyl)ethoxy]quinoline;

8-fluoro-4-[2-(2-methoxyphenyl)ethoxy]quinoline; and

8-fluoro-4-[2-(4-(i-propyl)phenyl)ethoxy]quinoline;

Compounds exhibiting particularly excellent activity as miticidesinclude:

8-fluoro-N-[2-(4-iodophenyl)ethyl]-4-quinolinamine;

N-[2-(4-bromophenyl)ethyl]-8-fluoro-4-quinolinamine;

N-[2-(4-chlorophenyl)ethyl)-8-fluoro-4-quinolinamine;

N-[2-(4-chlorophenyl)ethyl]-N-ethyl-8-fluoro-4-quinolinamine;

N-3-(1,1'-biphenyl)-4-ylpropyl]-8-fluoro-4-quinolin

8-fluoro-N-[2-(4-phenoxyphenyl)ethyl]-4-quinolinamine;

N-2-4-(t-butyl)phenyl]ethyl]-8-fluoro-4-quinolin

N-[2-[4-(i-propyl)phenyl]ethyl]-8-fluoro-4-quinolin

N-2-(4-chlorophenyl)ethyl]-6-fluoro-4-quinolinamine;

8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline;

4-[2-(3-chlorophenyl)ethoxy]-8-fluoroquinoline;

4-2-[4-(t-butyl)phenyl]ethoxy]-8-fluoroquinoline;

8-fluoro-4-[2-(4-(i-propyl)phenyl)ethoxy]quino

8-fluoro-4-2-(3-(trifluoromethyl)phenyl)ethoxy]quinoline;

8-fluoro-4-2-(4-methoxyphenyl)ethoxy]quinoline;

8-fluoro-4-2-(3-phenoxyphenyl)ethoxy]quinoline;

8-fluoro-4-2-(2-naphthyl)ethoxy]quinoline;

7-fluoro-4-2-(1,1'-biphenyl)-2-yl-ethoxy]quinoline;

7-chloro-4-[2-(1,1'-biphenyl)-4-yl-ethoxy]quinoline;

4-chloro-4-[2-(4-(t-butyl)phenyl)ethoxy]quinoline;

4-[2-(4-(t-butyl)phenyl)ethoxy]-7-fluoroquinoline;

8-2-(1,1'-biphenyl)-4-ylethoxy]-7-fluoroquinoline;

8-fluoro-4-(3-phenylpropyl)quinoline;

8-fluoro-4-[3-(4-methylphenyl)propyl]quinoline; and

8-fluoro-4-[3-[3-(trifluoromethyl)phenyl]propyl]quinoline.

Synthesis

The compounds of this invention are made using well known chemicalprocedures. The required starting materials are commercially available,or they are readily synthesized using standard procedures.

Synthesis of Compounds Wherein A is O--Y--Ar or --O--Alk

The compounds of formula (1) wherein A is O--Y--Ar or O--Alk were madeby condensing a compound of formula (3): ##STR4## where R¹ to R⁴ are aspreviously defined, R⁶, is H or CH₃, and W' is N or CR⁵ ', where R⁵ ' isH, Cl, or CH₃, with an alcohol of the formula (4a or 4b):

    HO--Y--Ar                                                  (4a)

    HO--Alk                                                    (4b)

where

Y, Ar, and Alk are as previously defined.

The reaction is preferably carried out in the presence of a strong base,such as sodium hydride, in an inert organic solvent, such as DMF, at atemperature in the range of 0° to 25° C.

Synthesis of Compounds Wherein A is NR⁷ --Y--Ar

The compounds of formula (1) wherein A is NR⁷ --Y--Ar were prepared bycondensing a compound of formula (3) with an amine of the formula (5)##STR5## where R⁷ is H or (C₁ -C₄) alkyl, and Y and

Ar are as previously defined.

The chloride of formula (3) is allowed to react with an appropriateamine, preferably at elevated temperature (100°-180° C.), and preferablyin the presence of an acid accepter, such as triethylamine. The reactionmay be carried out neat, or in an inert organic solvent.

Compounds where R⁷ is acetyl were prepared by reacting amines of formula(1) where R⁷ is H, with an acylating agent, such as an acetyl chlorideor acetic anhydride. In cases where the starting material of formula (3)is one wherein W' is CCl, a mixture of products is obtained, which areseparable using HPLC.

Synthesis of Compounds Wherein A is CR⁸ R⁹ --Y--Ar

The compounds of formula (1) wherein A is CR⁸ R⁹ --Y--Ar can be madeusing the process described in J. Heterocyclic Chemistry, Vol. 14, p.1081-1083 (1977) by A. Scoville and F. X. Smith. This process entailspreparation of a 5-substituted-5-(4-quinolyl)barbituric acid of theformula (6) ##STR6## which is then hydrolyzed and decarboxylated bydissolving the intermediate in a solution of sodium hydroxide and water,refluxing, then making the solution slightly acidic with hydrochloricacid and again refluxing.

Derivatives

The compounds of formula (1) wherein R⁶ is Cl are prepared byhalogenating a compound of formula (1) wherein R⁶ is H with POCl₃ /PCl₅.

The compounds of formula (1) wherein Rs is Br are prepared by reacting acompound of formula (1) wherein R⁶ is H with Br₂ in acetic acid.

N-oxides of the compounds of formula (1) are prepared by reacting thecompound of formula (1) with an oxidizing agent, such as3-chloroperoxybenzoic acid or hydrogen peroxide, in a non-reactiveorganic solvent, such as methylene chloride or chloroform, at -20° C. toroom temperature, preferably at about 0° C.

The acid addition salts of compounds of formula (1) are obtained in theusual way.

Accordingly, the invention also provides a process for preparing acompound of formula (1) which comprises:

(a) condensing a compound of formula (3): ##STR7## where R¹ to R⁴ are aspreviously defined, R⁶ ' is H or CH₃, and W' is N or CR⁵ ', where R⁵ 'is H, Cl, or CH₃, with an alcohol of the formula (4a or 4b):

    HO--Y--Ar,                                                 (4a)

    HO--Alk (4b)

where

Y, Ar, and Alk are as previously defined to provide a compound offormula (1) wherein A is O--Y--Ar or O--Alk; or

(b) condensing a compound of formula (3) with an amine of the formula(5) ##STR8## where R⁷ is H or (C₁ -C₄) alkyl, and Y and

Ar are as previously defined to provide a compound of formula (1)wherein A is --NR⁷ --Y--Ar; or

(c) reacting an amine of formula (1) where R⁷ is H, with acetyl chlorideor acetic anhydride to provide a compound of formula (1) wherein A is--NR⁷ --Y--Ar where R⁷ is acetyl; or

(d) hydrolyzing and decarboxylating a compound of the formula (6)##STR9## to provide a compound of formula (1) wherein A is --CR⁸ R⁹--Y--Ar or

(e) halogenating a compound of formula (1) wherein R⁶ is H with POCl₃/PCl₅ to provide a compound of formula (1) wherein R⁶ is Cl; or

(f) reacting a compound of formula (1) wherein R⁶ is H with Br₂ inacetic acid to provide a compound of formula (1) wherein R⁶ is Br; or

(g) oxidizing a compound of formula (1) wherein W is CRs to provide thecorresponding N-oxide.

Preparation of Quinoline Starting Materials

Quinoline starting materials can be synthesized using a variety of knownprocedures.

Organic Syntheses, collective volume 3, 1955, pp. 272-75, gives aprocedure for preparing 4,7-dichloroquinoline, and other polysubstitutedquinolines. Another general procedure is described in Tetrahedron, vol.41, pp. 3033-36 (1985).

Many of the quinoline starting materials used in the following exampleswere prepared by the protocol shown in the following reaction scheme##STR10##

In cases where mixtures of isomeric products were obtained, the mixtureof substituted 4-quinolones was chlorinated under standard conditions,and the 4-chloroquinolines were separated by liquid chromatography.

Preparation of Cinnoline Starting Materials

Cinnoline analogs are prepared via published methods. (C. M. Atkinsonand J. C. Simpson - J. Chem. Soc. London, 1947, 232). The substituted2-amino-acetophenone is diazotized at 0°-5° C. in water using sodiumnitrite and mineral acid, and the intermediate diazonium salt is trappedby the enolic component of the ketone to provide the requisite4-hydroxycinnoline. Routine chlorination provides the desiredintermediates.

EXAMPLES 1 TO 328

Tables 1-12 identify compounds actually prepared by the above describedgeneral procedures, and give each compound's melting point. Specificillustrative preparations of the compounds of Examples 4, 10, 25, 69,97, 154, 159, 173, 181, 186, 209, 212, 221, 238, 251, and 261 follow thetable.

                  TABLE 1                                                         ______________________________________                                        N-(2-phenylethyl)-4-quinolinamines                                            EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                         1       6-methoxy-N-(2-phenylethyl)-4-                                                                      NA                                                      quinolineamine                                                        2*      N-(2-phenylethyl)-4-quinolin-                                                                       159-160° C.                                      amine                                                                 3       6-ethyl-N-(2-phenylethyl)-4-                                                                        119-120° C.                                      quinolinamine                                                         4       N-ethyl-N-(2-phenylethyl)-4-                                                                        oil                                                     quinolinamine                                                         5       8-fluoro-N-(2-phenylethyl)-                                                                         149-150° C.                                      4-quinolinamine                                                       6       2-methyl-N-(2-phenylethyl)-                                                                         153-154° C.                                      4-quinolinamine                                                       7       6,8-difluoro-N-(2-phenylethyl)-                                                                     196-197° C.                                      ethyl)-4-quinolinamine                                                8       7-fluoro-N-(2-phenylethyl)-                                                                         160-161° C.                                      4-quinolinamine                                                       9       6-fluoro-N-(2-phenylethyl)-                                                                         163-164° C.                                      4-quinolinamine                                                      10       N-[2-(4-chlorophenyl)ethyl]-                                                                        oil                                                     N-(8-fluoro-4-quinolinyl)-                                                    acetamide                                                            11       8-fluoro-N-[2-(4-iodo-                                                                              221-223° C.                                      phenyl)ethyl]-4-quinolin-                                                     amine                                                                12       N-[2-(4-bromophenyl)ethyl]-                                                                         235-238° C.                                      6,8-difluoro-4-quinolinamine                                         13       N-[2-(4-bromophenyl)ethyl]-                                                                         188-190° C.                                      8-(trifluoromethyl)-4-quinolin-                                               amine                                                                14       N-[2-(4-chlorophenyl)ethyl]-                                                                        123-125° C.                                      6-methyl-4-quinolinamine                                             15       N-[2-(4-chlorophenyl)ethyl]-                                                                        113-115° C.                                      6,8-dimethyl-4-quinolinamine                                         16       N-[2-(4-chlorophenyl)ethyl]-                                                                        155-157° C.                                      6-methoxy-4-quinolinamine                                            17       N-(2-phenylethyl)-7-(tri-                                                                           138-139° C.                                      fluoromethyl)-4-quinolinamine                                        18       N-[2-(4-bromophenyl)ethyl]-                                                                         176-177° C.                                      4-quinolinamine                                                      19       N-[2-(4-methylphenyl)ethyl]-                                                                        159-160° C.                                      4-quinolinamine                                                      20*      N-[2-(4-chlorophenyl)ethyl]-                                                                        162-163° C.                                      4-quinolinamine                                                      21       N-(2-phenylpropyl)-4- 126-127°  C.                                     quinolinamine                                                        22       N-[2-(4-methoxyphenyl)-                                                                             127-128° C.                                      ethyl]-4-quinolinamine                                               23       N-(2,2-diphenylethyl)-4-                                                                            154-155° C.                                      quinolinamine                                                        24       N-(1-methyl-2-phenylethyl)-                                                                         132-133° C.                                      4-quinolinamine                                                      25       2-chloro-N-(2-phenylethyl)-                                                                         132-133° C.                                      4-quinolinamine                                                      26       α-[(4-quinolinylamino)-                                                                       195-197° C.                                      methyl]benzenemethanol                                               27       8-methyl-N-(2-phenylethyl)-                                                                         127-128° C.                                      4-quinolinamine                                                      28       6,8-dimethyl-N-(2-phenyl-                                                                           114-115° C.                                      ethyl)-4-quinolinamine                                               29       8-ethyl-N-(2-phenyl)-  98-99° C.                                       4-quinolinamine                                                      30       6-methyl-N-(2-phenylethyl)-                                                                         124-125° C.                                      4-quinolinamine                                                      31       7-chloro-N-(2-phenylethyl)-                                                                         137-138° C.                                      4-quinolinamine                                                      32       7,8-dimethyl-N-(2-phenyl-                                                                           183-185° C.                                      ethyl)-4-quinolinamine                                               33       8-chloro-N-(2-phenylethyl)-                                                                         156-157° C.                                      4-quinolinamine                                                      34       N-(2,2-diphenylpropyl)-4-                                                                           110-111° C.                                      quinolinamine                                                        35       N-[2-(4-fluorophenyl)ethyl]-                                                                        121-122° C.                                      4-quinolinamine                                                      36       8-fluoro-N-[2-(4-methoxy-                                                                           165-167° C.                                      phenyl)ethyl]-4-quinolinamine                                        37       7-chloro-N-[2-(4-chloro-                                                                            190-192° C.                                      phenyl)ethyl]-4-quinolinamine                                        38       N-[2-(3,4-dimethoxyphenyl)-                                                                         127-130° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                39       8-fluoro-N-[2-(3-phenoxy-                                                                            83-85° C.                                       phenyl)ethyl]-4-quinolin-                                                     amine                                                                40       6,8-difluoro-N-(2-[1,1'-                                                                            216-218° C.                                      biphenyl]-4-ylethyl)-4-                                                       quinolinamine                                                        41       N-[2-(4-chlorophenyl)ethyl]-                                                                        218-220° C.                                      6,8-difluoro-4-quinolinamine                                         42       N-[2-(4-methoxyphenyl)ethyl]-                                                                       107-109° C.                                      7-(trifluoromethyl)-4-quinolin-                                               amine                                                                43       7-chloro-N-[2-(3-methoxy-                                                                           155-158° C.                                      phenyl)ethyl]-4-quinolinamine                                        44       7-chloro-N-[2-(2,4-dichloro-                                                                        168-170° C.                                      phenyl)ethyl]-4-quinolinamine                                        45       7-chloro-N-[2-(3,5-di-                                                                              117-120° C.                                      methoxyphenyl)ethyl]-4-                                                       quinolinamine                                                        46       N-[2-(4-methoxyphenyl)-                                                                             120-123° C.                                      ethyl]-6-methyl-4-quinolin-                                                   amine                                                                47       N-[2-(4-chlorophenyl)ethyl]-                                                                        153-155° C.                                      7-(trifluoromethyl)-4-quinolin-                                               amine                                                                48       N-[2-(3,4-dimethoxyphenyl)-                                                                         oil                                                     ethyl]-7-(trifluoromethyl)-4-                                                 quinolinamine                                                        49       N-[2-(3-chlorophenoxy)ethyl]-                                                                       161-163° C.                                      8-fluoro-4-quinolinamine                                             50       7-chloro-N-[2-(4-methyl-                                                                            155-158° C.                                      phenyl)ethyl]-4-quinolinamine                                        51       8-chloro-N-[2-(4-fluoro-                                                                            194-196° C.                                      phenyl)ethyl]-4-quinolinamine                                        52       N-[2-(2,4-dichlorophenyl)-                                                                          158-160° C.                                      ethyl]-8-(trifluoromethyl)-4-                                                 quinolinamine                                                        53       N-[2-(2,4-dichlorophenyl)-                                                                          180-182° C.                                      ethyl]-6-methyl-4-quinolinamine                                      54       7-chloro-6-methoxy-2-methyl-                                                                        180-181° C.                                      N-(2-phenylethyl)-4-quinolin-                                                 amine                                                                55       N-[2-(2-methoxyphenyl)-                                                                             127-128° C.                                      ethyl]-4-quinolinamine                                               56       N-[2-(4-chlorophenyl)ethyl]-                                                                        134-138° C.                                      6-fluoro-4-quinolinamine                                             57       N-[2-(4-chlorophenyl)ethyl]-                                                                        104-106° C.                                      2-methyl-6-fluoro-4-quinolin-                                                 amine                                                                58       6-methyl-N-[2-(4-methyl-                                                                            122-124° C.                                      phenyl)ethyl]-4-quinolinamine                                        59       5,7-dichloro-N-[2-(4-chloro-                                                                        113-115° C.                                      phenyl)ethyl]-4-quinolinamine                                        60       7-chloro-N-[2-(3-phenoxy-                                                                           128-130° C.                                      phenyl)ethyl]-4-quinolinamine                                        61       8-methyl-N-[2-(4-chloro-                                                                            118-120° C.                                      phenyl)ethyl] -4-quinolinamine                                       62       8-fluoro-N-(2-cyclohexyl-2-                                                                          74-75° C.                                       phenylethyl)-4-quinolinamine                                         63       8-fluoro-N-[2-(2-phenoxyphenyl)-                                                                    131-133° C.                                      ethyl]-4-quinolinamine                                               64       7,8-dimethyl-N-[2-(2-phenoxyphenyl)-                                                                124-126° C.                                      ethyl]-4-quinolinamine                                               65       N-[2-(2,6-difluorophenyl)-                                                                          203-204° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                66       8-fluoro-N-[2-(3-fluoro-                                                                            174-175° C.                                      phenyl)ethyl]-4-quinolinamine                                        67       N-[2-(3,5-dimethoxyphenyl)-                                                                         122-123° C.                                      ethyl]-4-quinolinamine                                               68       8-fluoro-N-[2-(2-methoxy-                                                                           163-164° C.                                      phenyl)ethyl]-4-quinolinamine                                        69       3-chloro-N-(2-chloro-2-                                                                             oil                                                     phenylethyl)-4-quinolinamine                                         70       N-(2-phenylethyl)-5,7-bis-                                                                          oil                                                     (trifluoromethyl)-4-quinolin-                                                 amine                                                                71       8-fluoro-N-[2-(4-methyl-                                                                            176-177° C.                                      phenyl)ethyl]-4-quinolin-                                                     amine                                                                72       N-[2-(1,1'-biphenyl)-3-ylethyl]-                                                                    140-142° C.                                      8-fluoro-4-quinolinamine                                             73       8-fluoro-4-[(2-phenylethyl)-                                                                        107-108° C.                                      amino]-3-quinolinemethanol                                           74       N-[2-(3-chlorophenyl)ethyl]-                                                                        191-192° C.                                      8-fluoro-4-quinolinamine                                             75       N-[2-(3,4-dichlorophenyl)-                                                                          204-206° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                76       N-[2-(2,4-dichlorophenyl)-                                                                          187-189° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                77       8-fluoro-N-(2-phenylpropyl)-                                                                        136-137° C.                                      4-quinolinamine                                                      78       8-fluoro-N-[2-(4-fluoro-                                                                            171-173° C.                                      phenyl)ethyl]-4-quinolinamine                                        79       N-[2-(4-chlorophenyl)-                                                                              126-127° C.                                      propyl]-8-fluoro-4-quinolin-                                                  amine                                                                80       N-(2,2-diphenylpropyl)-8-                                                                            56-58° C.                                       fluoro-4-quinolinamine                                               81       8-fluoro-N-(2-phenylbutyl)-                                                                         114-116° C.                                      4-quinolinamine                                                      82       N-[2-(2-chlorophenyl)ethyl]-                                                                        175-177° C.                                      8-fluoro-4-quinolinamine                                             83       8-fluoro-N-[2-[4-(trifluoro-                                                                        205-206° C.                                      methyl)phenyl]ethyl]-4-                                                       quinolinamine                                                        84       7-chloro-N-[2-(4-methoxy-                                                                           122-124° C.                                      phenyl)ethyl]-4-quinolinamine                                        85       8-chloro-N-[2-(4-chloro-                                                                            185-187° C.                                      phenyl)ethyl]-4-quinolinamine                                        86       N-[2-(4-chlorophenyl)ethyl]-                                                                        192-194° C.                                      8-(trifluoromethyl)-4-quinolin-                                               amine                                                                87       8-chloro-N-[2-(4-methyl-                                                                            184-186° C.                                      phenyl)ethyl]-4-quinolinamine                                        88       N-[2-(4-chlorophenyl)ethyl]-                                                                        177-179° C.                                      7,8-dimethyl-4-quinolinamine                                         89       8-fluoro-N-[2-(4-methyl-                                                                            153-154° C.                                      phenyl)ethyl]-4-quinolinamine                                        90       8-fluoro-N-[2-(4-phenoxy-                                                                           109-111° C.                                      phenyl)ethyl]-4-quinolin-                                                     amine                                                                91       3-bromo-8-fluoro-N-(2-phenyl-                                                                        95-97° C.                                       ethyl)-4-quinolinamine                                               92       8-fluoro-N-(1-methyl-2-                                                                             166-168° C.                                      phenylethyl)-4-quinolinamine                                         93       2,8-dichloro-N-(2-phenyl-                                                                           190-192° C.                                      ethyl)-4-quinolinamine                                               94       N-[2-(4-bromophenyl)ethyl]-                                                                         198-199° C.                                      8-fluoro-4-quinolinamine                                             95       8-fluoro-N-[2-[3-(trifluoro-                                                                        161-162° C.                                      methyl)phenyl]ethyl]-4-                                                       quinolinamine                                                        96       N-[2-(4-chlorophenyl)ethyl)-                                                                        176-177° C.                                      8-fluoro-4-quinolinamine                                             97       8-fluoro-N-[2-[2-(trifluoro-                                                                        157-158° C.                                      methyl)phenyl]ethyl]-4-                                                       quinolinamine                                                        98       2-chloro-N-[2-(2,4-dichloro-                                                                        199-200° C.                                      phenyl)ethyl]-8-fluoro-4-                                                     quinolinamine                                                        99       N-(2-phenylethyl)-8-(tri-                                                                           151-152° C.                                      fluoromethyl)-4-quinolin-                                                     amine                                                                100      7-chloro-N-[2-(2-methoxy-                                                                           140-142°                                         phenyl)ethyl]-4-quinolinamine                                        101      7-chloro-N-[2-(3,4-dichloro-                                                                        128- 130° C.                                     phenyl)ethyl]-4-quinolinamine                                        102      N-[2-(4-chlorophenyl)ethyl]-                                                                        176-178° C.                                      2-methyl-4-quinolinamine                                             103      N-[2-(2-chloro-6-fluoro-                                                                            198-201° C.                                      phenyl)ethyl]-8-fluoro-4-                                                     quinolinamine                                                        104      N-[2-(2,4-dichlorophenyl)-                                                                          175-177° C.                                      ethyl]-7-(trifluoromethyl)-                                                   4-quinolinamine                                                      105      N-[2-(4-chlorophenyl)ethyl]-                                                                        oil                                                     N-ethyl-8-fluoro-4-quinolin-                                                  amine                                                                106      7-chloro-N-(4-fluorophenyl)-                                                                         83-85° C.                                       N-methyl-4-quinolinamine                                             107      7-chloro-N-[2-[3-(trifluoro-                                                                        184-186° C.                                      methyl)phenyl]ethyl]-4-                                                       quinolinamine                                                        108      N-[2-(3-bromophenyl)ethyl]-                                                                         206-208° C.                                      8-fluoro-4-quinolinamine                                             109      N-[2-(4-chlorophenyl)ethyl]-5,8-                                                                    oil                                                     dimethyl-4-quinolinamine                                             110      N(4)-[2-(4-chlorophenyl)ethyl]-                                                                     oil                                                     4,8-quinolinamine                                                    111      N-[2-[4-( .sub.- t-butyl)phenyl]ethyl]-                                                             198-200° C.                                      8-fluoro-4-quinolinamine                                             112      N-[2-(2,3,4,5,6-tetramethyl-                                                                        204-207° C.                                      phenyl)ethyl]-8-fluoro-4-                                                     quinolinamine                                                        113      N-[2-(1,1-biphenyl)-4-yl-                                                                           178-180° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                114      N-[2-[4-( .sub.- i-propyl)phenyl]ethyl]-                                                            157-159° C.                                      8-fluoro-4-quinolinamine                                             115      N-[2-(2-chlorophenyl)ethyl]-                                                                        205-207° C.                                      8-chloro-4-quinolinamine                                             116      2-chloro-8-fluoro-N-(2-                                                                             158-159° C.                                      phenylethyl)-4-quinolinamine                                         117      8-fluoro-N-[2-(4-nitro-                                                                             234-236° C.                                      phenyl)ethyl]-4-quinolin-                                                     amine                                                                118      N-[2-(2,6-dichlorophenyl)-                                                                          222-224° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                119      N-[2-(3,5-dimethoxyphenyl)-                                                                         131-132° C.                                      ethyl]-8-fluoro-4-quinolin-                                                   amine                                                                120      N-(2-phenylcyclopropyl)-4-                                                                          147-148° C.                                      quinolinamine                                                        121      N-[2-(4-chlorophenyl)ethyl]-N-                                                                       87-88° C.                                       (6-fluoro-4-quinolinyl)acetamide                                     122      N-[2-(4-methylphenyl)ethyl]-N-                                                                       97-98° C.                                       (6-methyl-4-quinolinyl)acetamide                                     123      8-fluoro-N-(2-phenylcyclopropyl)-4-                                                                 204-205° C.                                      quinolinamine                                                        124      N-[2-(4-chlorophenyl)ethyl]-N-(7-                                                                   oil                                                     chloro-4-quinolinyl)acetamide                                        125      N-(7-chloro-4-quinolinyl)-N-[2-(4-                                                                  oil                                                     methoxyphenyl)ethyl]acetamide                                        126      N-(7-chloro-4-quinolinyl)-N-[2-[3-                                                                  oil                                                     (trifluoromethyl)phenyl]ethyl]-                                               acetamide                                                            127      N-[2-(2,4-dichlorophenyl)ethyl]-N-                                                                  oil                                                     [7-(trifluoromethyl)-4-quinolinyl]-                                           acetamide                                                            128      N-[4-( .sub.- t-butyl)phenyl]ethyl-N-(8-                                                            126-128° C.                                      fluoro-4-quinolinyl)acetamide                                        129      N-[2-[4-( .sub.- i-propyl)phenyl]ethyl]-                                                             82-84° C.                                       N-(8-fluoro-4-quinolinyl)acetamide                                   130      N-[2-(1,1'-biphenyl)-4-ylethyl]-N-                                                                  oil                                                     (8-fluoro-4-quinolinyl)acetamide                                     131      N-[2-(pentamethylphenyl)ethyl]-N-                                                                   oil                                                     (8-fluoro-4-quinolinyl)acetamide                                     132      N-[2-(2-chlorophenyl)ethyl]-N-(8-                                                                   104-106° C.                                      chloro-4-quinolinyl)acetamide                                        133      N-[2-(4-methoxyphenyl)ethyl]-7,8-                                                                   183-185° C.                                      dimethyl-4-quinolinamine                                             ______________________________________                                         *not a compound claimed per se, but one used in the claimed compositions      and methods.                                                             

                  TABLE 2                                                         ______________________________________                                        N-(3-phenylpropyl)-4-quinolinamines                                           EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        134      7-chloro-N-[3-(1,1'-biphenyl)-4-                                                                    122-124° C.                                      ylpropyl]-4-quinolinamine                                            135      N-[3-(4-chlorophenyl)propyl]-8-                                                                     134-136° C.                                      fluoro-4-quinolinamine                                               136      N-[3-(4-chlorophenyl)propyl]-7-                                                                     177-179° C.                                      chloro-4-quinolinamine                                               137      N-[3-(1,1'-biphenyl)-4-ylpropyl]-                                                                   124-127° C.                                      8-fluoro-4-quinolinamine                                             138      8-fluoro-N-(1-methyl-3-phenylpropyl)-                                                               164-166° C.                                      4-quinolinamine                                                      139      N-(3-phenylpropyl)-4-quinolinamine                                                                   96-97° C.                              ______________________________________                                    

                  TABLE 3                                                         ______________________________________                                        N-(4-phenylbutyl)-4-quinolinamines                                            EXAMPLE                                                                       NUMBER   COMPOUND             M.P.                                            ______________________________________                                        140      8-fluoro-N-[4-(4-chlorophenyl)-                                                                    110-112° C.                                       butyl]-4-quinolinamine                                               141      N-[4-(4-chlorophenyl)butyl]-N-(8-                                                                  oil                                                      fluoro-4-quinolinyl)acetamide                                        ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        N-Arylalkyl-4-quinolinamines                                                  EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        142      N-[2-(1-cyclohexenyl)ethyl]-5,8-                                                                    78-81° C.                                        dimethyl-4-quinolinamine                                             143      N-[2-(1-cyclohexenyl)ethyl]-8-                                                                      153-155° C.                                      fluoro-4-quinolinamine                                               144      N-[2-(1-cyclohexenyl)ethyl]-6,8-                                                                    114-116° C.                                      dimethyl-4-quinolinamine                                             145      N-[2-(1-cyclohexenyl)ethyl]-6-                                                                      135-137° C.                                      ethyl-4-quinolinamine                                                146      N-[2-(1-cyclohexenyl)ethyl]-N-                                                                      66-68° C.                                        (6-fluoro-4-quinolinyl)acetamide                                     147      N-[2-(2-thienyl)ethyl]-4-quinolin-                                                                  153-154° C.                                      amine                                                                148      N-[2-(3-thienyl)ethyl]-4-quinolin-                                                                  156-157° C.                                      amine                                                                149      6,8-difluoro-N-[2-(2-thienyl)ethyl]-                                                                175-176° C.                                      4-quinolinamine                                                      150      6,8-difluoro-N-[2-(3-thienyl)ethyl]-                                                                191-192° C.                                      4-quinolinamine                                                      151      N-[2-(1-naphthyl)ethyl]-4-                                                                          149-150° C.                                      quinolinamine                                                        152      N-[2-(2-naphthyl)ethyl]-4-                                                                          160-161° C.                                      quinolinamine                                                        153      N-[2-(2-thienyl)ethyl]-7-(trifluoro-                                                                131-132° C.                                      methyl)-4-quinolinamine                                              154      8-fluoro-N-[2-(4-phenyl-2-thiazolyl)-                                                               134-135° C.                                      ethyl]-4-quinolinamine                                               155      8-chloro-N-[2-(1-naphthyl)ethyl]-                                                                   205-206° C.                                      4-quinolinamine                                                      156      8-chloro-N-[2-(2-naphthyl)ethyl]-                                                                   206-208° C.                                      4-quinolinamine                                                      157      α-[[(8-fluoro-4-quinolinyl)amino]-                                                            182-185° C.                                      methyl]-2-naphthalenemethanol                                        158      8-fluoro-N-[2-(1-naphthyl)ethyl]-                                                                   152-153° C.                                      4-quinolinamine                                                      159      8-fluoro-N-[2-(2-naphthyl)ethyl]-                                                                   173-174° C.                                      4-quinolinamine                                                      160      N-[2-(1-cyclohexenyl)ethyl]-N-(5,8-                                                                 oil                                                     dimethyl-4-quinolinyl)acetamide                                      161      N-(2-cyclohexylethyl)-N-(8-fluoro-                                                                  oil                                                     4-quinolinyl)acetamide                                               162      8-fluoro-N-[2-(5-methyl-2-thienyl)-                                                                 161-163° C.                                      ethyl]-4-quinolinamine                                               163      N-[2-(5-chloro-2-thienyl)ethyl]-8-                                                                  167-168° C.                                      fluoro-4-quinolinamine                                               164      8-fluoro-N-[2-(1H-imidazol-4-yl)-                                                                   230° C.                                          ethyl]-4-quinolinamine                                               165      7-chloro-N-[2-(1-cyclohexenyl)-                                                                     161-163° C.                                      ethyl]-4-quinolinamine                                               166      7-chloro-N-[2-(2-naphthyl)-                                                                         156-158° C.                                      ethyl]-4-quinolinamine                                               167      N-[2-(1-cyclohexenyl)ethyl]-7-                                                                      158-160° C.                                      (trifluoromethyl)-4-quinolinamine                                    168      N-[2-(1-cyclohexenyl)ethyl]-6-                                                                      129-131° C.                                      fluoro-4-quinolinamine                                               169      N-[2-(2-naphthyl)ethyl]-7-(tri-                                                                     127-130° C.                                      fluoromethyl)-4-quinolinamine                                        170      8-fluoro-N-[1-methyl-2-(2-thienyl)-                                                                 217-219° C.                                      ethyl]-4-quinolinamine                                               171      N-[1-methyl-2-(2-thienyl)ethyl]-                                                                    167-168° C.                                      4-quinolinamine                                                      172      8-chloro-N-[2-(2-thienyl)ethyl]-4-                                                                  161-162° C.                                      quinolinamine                                                        173      8-fluoro-N-[2-(2-thienyl)ethyl]-4-                                                                  157-158° C.                                      quinolinamine                                                        174      N-[2-(2,3-dihydro-1,4-benzodioxin-                                                                  170-171° C.                                      2-yl)ethyl]-8-fluoro-4-quinolinamine                                 175      8-fluoro-N-[2-(3-thienyl)ethyl]-4-                                                                  163-164° C.                                      quinolanamine                                                        176      8-fluoro-N-[2-(1H-indol-3-yl)ethyl]-                                                                205-206° C.                                      4-quinolinamine                                                      177      N-(2-cyclohexylethyl)-8-fluoro-4-                                                                   145-147° C.                                      quinolinamine                                                        178      N-(2-cyclohexylethyl)-6,8-dimethyl-                                                                 155-157° C.                                      4-quinolinamine                                                      179      N-[2-(1-cyclohexenyl)ethyl]-N-(6,8-                                                                 oil                                                     dimethyl-4-quinolinyl)acetamide                                      180      8-fluoro-N-[2-(2-pyridinyl)ethyl]-                                                                  143-144° C.                                      4-quinolinamine                                                      ______________________________________                                    

                  TABLE 5                                                         ______________________________________                                        Bis[2-phenylethyl]quinolinediamines                                           EXAM-                                                                         PLE                                                                           NUMBER  COMPOUND               M.P.                                           ______________________________________                                        181     N,N'-bis(2-phenylethyl)-2,4-                                                                         70-71° C.                                       quinolinediamine                                                      182     N,N'-(2,4-quinolinediyl)bis[N-[2-(4-                                                                 oil                                                    chlorophenyl)ethyl]acetamide]                                         183     8-fluoro-N,N'-bis(2-phenylethyl)-2,4-                                                                oil                                                    quinolinediamine                                                      184     N,N'-bis(2-phenylpropyl)-2,4-quinoline-                                                              oil                                                    diamine                                                               185     N,N'-bis[2-(4-chlorophenyl)ethyl]-                                                                   135-137° C.                                     4,6-quinolinediamine                                                  186     N,N'-bis[2-(4-chlorophenyl)ethyl]-4,7-                                                               55-60° C.                                       quinolinediamine                                                      187     N,N'-bis[2-(4-methoxyphenyl)ethyl]-                                                                  140-150° C.                                     4,7-quinolinediamine                                                  188     N,N'-bis[2-(4-chlorophenyl)ethyl]-8-                                                                 oil                                                    fluoro-2,4-quinolinediamine                                           189     N,N'-bis(2-phenylethyl)-4,8-quinoline-                                                               83-84° C.                                       diamine                                                               190     N,N'-bis[2-(2,4-dichlorophenyl)ethyl]-                                                               116-117° C.                                     8-fluoro-2,4-quinolinediamine                                         191     N,N'-(4,7-quinolinediyl)bis[N-[2-(4-                                                                 oil                                                    chlorophenyl)ethyl]acetamide]                                         ______________________________________                                    

                  TABLE 6                                                         ______________________________________                                        Bis[2-arylethyl]quinolinediamines                                             EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        192      N,N'-bis[2-(1-cyclohexen-yl)ethyl]-                                                                 129-131° C.                                      4,6-quinolinediamine                                                 ______________________________________                                    

                  TABLE 7                                                         ______________________________________                                        4-(2-phenylethoxy)quinolines                                                  EXAM-                                                                         PLE                                                                           NUMBER  COMPOUND               M.P.                                           ______________________________________                                        193     2-chloro-8-fluoro-4-[2-(4-methyl-                                                                    76-77° C.                                       phenyl)ethoxy]quinoline                                               194     5,7-dichloro-4-[2-(1,1'-biphenyl)-                                                                   100-102° C.                                     4-ylethoxy]quinoline                                                  195     4-[2-(3-methoxyphenyl)ethoxy]-8-                                                                     90-91° C.                                       fluoroquinoline                                                       196     8-fluoro-4-[2-(4-methoxyphenyl)-                                                                     70-71° C.                                       ethoxy]quinoline                                                      197     8-fluoro-4-[2-(3-phenoxyphenyl)-                                                                     73-75° C.                                       ethoxy]quinoline                                                      198     8-bromo-4-[2-(4-( .sub.- t-butyl)phenyl)-                                                            115-118° C.                                     ethoxy]quinoline                                                      199     4-[2-(3,4-dimethoxyphenyl)ethoxy]-8-                                                                 113-114° C.                                     fluoroquinoline                                                       200     8-fluoro-N-[2-(1,1'-biphenyl)-4-yl-                                                                  141-142° C.                                     ethoxy]quinoline                                                      201     4-[2-(3-chlorophenyl)ethoxy]-8-fluoro-                                                               76-77° C.                                       quinoline                                                             202     7-chloro-4-(2-phenylethoxy)quinoline                                                                 oil                                            203     8-fluoro-4-[2-(3-(trifluoromethyl)-                                                                  98-99° C.                                       phenyl)ethoxy]quinoline                                               204     7-chloro-4-[2-(4-methylphenyl)ethoxy]-                                                               87-88° C.                                       quinoline                                                             205     8-fluoro-4-[2-(2-methylphenyl)ethoxy]-                                                               72° C.                                          quinoline                                                             206     8-fluoro-4-[2-(2-(trifluoromethyl)-                                                                  60° C.                                          phenyl)ethoxy]quinoline                                               207     8-chloro-4-(2-phenylethoxy)quinoline                                                                 73-74° C.                               208     4-(2-phenylethoxy)quinoline                                                                          oil                                            209     4-[2-(4-chlorophenyl)ethoxy]-8-fluoro-                                                               138-140° C.                                     quinoline                                                             210     4-[2-(4-methylphenyl)ethoxy]quinoline                                                                59-60° C.                               211     4-[2-(4-chlorophenyl)ethoxy]quinoline                                                                106-107° C.                             212     8-fluoro-4-[2-(4-methylphenyl)ethoxy]-                                                               89-90°  C.                                      quinoline                                                             213     4-(1-methyl-2-phenylethoxy)quinoline                                                                 oil                                            214     8-fluoro-4-[1-(phenylmethyl)ethoxy]-                                                                 oil                                                    quinoline                                                             215     8-bromo-4-[2-(4-chlorophenyl)ethoxy]-                                                                112-114° C.                                     quinoline                                                             216     8-chloro-4-[2-(2-chlorophenyl)ethoxy]-                                                               90-92° C.                                       quinoline                                                             217     8-fluoro-4-[2-(2-(1-methylethyl)phenyl)-                                                             oil                                                    ethoxy]quinoline                                                      218     8-fluoro-4-[2-(3-(phenylthio)phenyl)-                                                                oil                                                    ethoxy]quinoline                                                      219     8-fluoro-4-(2-phenylethoxy)quinoline                                                                 63-65° C.                               220     4-(2-phenylpropoxy)-8-fluoroquinoline                                                                oil                                            221     4-[2-[4-( .sub.- t-butyl)phenyl]ethoxy]-                                                             81-82° C.                                       8-fluoroquinoline                                                     222     8-fluoro-4-[2-(4-fluorophenyl)-                                                                      126-127° C.                                     ethoxy]quinoline                                                      223     4-[2-(4-bromophenyl)ethoxy]-8-                                                                       130° C.                                         fluoroquinoline                                                       224     8-fluoro-4-[2-(3-methylphenyl)ethoxy]-                                                               92° C.                                          quinoline                                                             225     8-fluoro-4-[2-(2-fluorophenyl)ethoxy]-                                                               75° C.                                          quinoline                                                             226     7-chloro-4-[2-(4-chlorophenyl)ethoxy]-                                                               96-97° C.                                       quinoline                                                             227     8-fluoro-4-[2-(2,4,6-trimethylphenyl)-                                        ethoxy]quinoline                                                      228     8-fluoro-4-[2-(2-methoxyphenyl)ethoxy]-                                                              74-75° C.                                       quinoline                                                             229     4-[2-(2-methoxyphenyl)ethoxy]quinoline                                                               oil                                            230     7-chloro-4-[2-(1,1'-biphenyl)-4-yl-                                                                  95-96° C.                                       ethoxy]quinoline                                                      231     7-chloro-4-[2-(4-( .sub.- t-butyl)phenyl)-                                                           123-124° C.                                     ethoxy]quinoline                                                      232     4-[2-(4-( .sub.- t-butyl)phenyl)ethoxy]-7-                                                           98-99° C.                                       fluoroquinoline                                                       233     4-[2-(1,1'-biphenyl)-4-ylethoxy]-7-                                                                  73-75° C.                                       fluoroquinoline                                                       234     4-[2-(4-chlorophenyl)ethoxy] -7-fluoro-                                                              81-82° C.                                       quinoline                                                             235     7-fluoro-4-[2-(4-methylphenyl)ethoxy]-                                                               85-86° C.                                       quinoline                                                             236     7-chloro-4-[2-(4-fluorophenyl)ethoxy]-                                                               80° C.                                          quinoline                                                             237     8-fluoro-4-[2-(1,1'-biphenyl)-2-yl-                                                                  55-60° C.                                       ethoxy]quinoline                                                      238     8-fluoro-4-[2-(4-( .sub.- i-propyl)phenyl)-                                                          59-60° C.                                       ethoxy]quinoline                                                      239     4-(2-phenylethoxy)-7-(trifluoro-                                                                     55-57° C.                                       methyl)quinoline                                                      240     8-chloro-4-[2-(4-fluorophenyl)-                                                                      125-127° C.                                     ethoxy]quinoline                                                      ______________________________________                                    

                  TABLE 8                                                         ______________________________________                                        4-(3-phenylpropoxy)quinolines                                                 EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        241      8-fluoro-4-[3-[4-( .sub.- t-butyl)phenyl]-                                                          103-105° C.                                      propoxy]quinoline                                                    242      8-chloro-4-[3-(4-chlorophenyl)-                                                                     117-119° C.                                      propoxy]quinoline                                                    243      8-fluoro-4-[(3-phenyl-2-propenyl)-                                                                  128-130° C.                                      oxy]quinoline                                                        ______________________________________                                    

                  TABLE 9                                                         ______________________________________                                        4-(2-Arylethoxy)quinolines                                                    EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        244      8-fluoro-4-[2-(1-naphthyl)-                                                                         121-122° C.                                      ethoxy]quinoline                                                     245      4-[2-(2-thienyl)ethoxy]-                                                                            oil                                                     quinoline                                                            246      8-fluoro-4-[2-(2-thienyl)-                                                                          77-79° C.                                        ethoxy]quinoline                                                     247      8-fluoro-4-[2-(2-naphthyl)ethoxy]-                                                                  123-124° C.                                      quinoline                                                            248      5-chloro-4-(2-cyclohexylethoxy)-2,8-                                                                100-102° C.                                      dimethylquinoline                                                    249      6-fluoro-4-(2-cyclohexylethoxy)-2-                                                                  113-115° C.                                      methylquinoline                                                      ______________________________________                                    

                  TABLE 10                                                        ______________________________________                                        Bis(2-phenylethoxy)quinolines                                                 EXAMPLE                                                                       NUMBER   COMPOUND              M.P.                                           ______________________________________                                        250      8-fluoro-2,4-bis[2-(4-methyl-                                                                       125-126° C.                                      phenyl)ethoxy]quinoline                                              251      4,8-bis[2-(4-methylphenyl)ethoxy]-                                                                  142-143° C.                                      quinoline                                                            ______________________________________                                    

                  TABLE 11                                                        ______________________________________                                        4-(3-Arylpropyl)quinolines                                                    EXAMPLE                                                                       NUMBER   COMPOUND               M.P.                                          ______________________________________                                        252      4-(3-phenylpropyl)quinoline                                          253      8-fluoro-4-(3-phenylpropyl)quinoline                                                                 43-45° C.                              254      4-(3-phenylpropyl)-7-(trifluoro-                                                                     oil                                                    methyl)quinoline                                                     255      8-chloro-4-(3-phenylpropyl)quinoline                                                                 70-71° C.                              256      8-fluoro-4-[3-(4-( .sub.- i-propyl)phenyl)-                                                          oil                                                    propyl]quinoline                                                     257      4-[3-(1,1'-biphenyl)-4-ylpropyl]-8-                                                                  oil                                                    fluoroquinoline                                                      258      8-fluoro-4-[3-(4-methylphenyl)propyl)]-                                                              oil                                                    quinoline                                                            259      8-fluoro-4-[3-[3-(trifluoromethyl)-                                                                  65-66° C.                                       phenyl]propyl]quinoline                                              260      4-[3-[4-( .sub.- t-butyl)phenyl]propyl]-8-                                                           oil                                                    fluoroquinoline                                                      261      4-[3-(4-chlorophenyl)propyl]-8-fluoro-                                                               97° C.                                          quinoline                                                            ______________________________________                                    

                  TABLE 12                                                        ______________________________________                                        Additional Compounds                                                          EXAM-                                                                         PLE                                                                           NUMBER  COMPOUND               M.P.                                           ______________________________________                                        262     4-[2-[4-( .sub.- t-butyl)phenyl]ethoxy]-                                                             67-69° C.                                       quinoline                                                             263     8-fluoro-4-[2-(1,1'-biphenyl)-4-yl-                                                                  97-99° C.                                       ethoxy]quinoline                                                      264     8-fluoro-4-[(2-phenylethyl)sulfinyl]-                                                                NA                                                     quinoline                                                             265     8-fluoro-4-[2-[4-(2-hydroxyethyl)-                                                                   NA                                                     phenyl]ethoxy]quinoline                                               266     8-fluoro-4-[3-methoxybutoxy]-                                                                        oil                                                    quinoline                                                             267     8-fluoro-4-(4-pentenoxy)quinoline                                                                    75-78° C.                               268     8-fluoro-N-(4-phenylbutyl)-4-                                                                        104-106° C.                                     quinolinamine                                                         269     4-[2-(2-chlorophenyl)ethoxy]-8-                                                                      78-80° C.                                       fluoroquinoline                                                       270     4-[2-[1,1'-biphenyl]-4-ylbutoxy]-8-                                                                  oil                                                    fluoroquinoline                                                       271     N-[3-[4-( .sub.- t-butyl)phenyl]propyl]-8-                                                           oil                                                    fluoro-4-quinolinamine                                                272     8-fluoro-4-(4-phenoxybutoxy)quinoline                                                                87-89° C.                               273     N-[2-(4-acetoxyphenyl)ethyl]-N-(8-                                                                   oil                                                    fluoro-4-quinolinyl)acetamide                                         274     8-fluoro-4-(3,5,5-trimethylhexyloxy)-                                                                oil                                                    quinoline                                                             275     8-fluoro-4-[2-(2,4-difluorophenyl)-                                                                  98-100° C.                                      ethoxy]quinoline                                                      276     7-chloro-4-[2-(2,4-difluorophenyl)-                                                                  103-105° C.                                     ethoxy]quinoline                                                      277     5,7-dichloro-4-[2-(4-ethoxyphenyl)-                                                                  104-105° C.                                     ethoxy]quinoline                                                      278     4-[2-(4-butoxyphenyl)ethoxy]-8-                                                                      80-82° C.                                       fluoroquinoline                                                       279     6-ethoxy-2-methyl-4-[3-(phenyl-                                                                      38-40° C.                                       methoxy)propoxy]quinoline                                             280     8-chloro-N-[2-(3-phenoxyphenyl)-                                                                     145-147° C.                                     ethyl]-4-quinolinamine                                                281     8-chloro-N-(4-phenylbutyl)-4-quino-                                                                  134-136° C.                                     linamine                                                              282     8-fluoro-4-[3-(4-phenoxyphenyl)pro-                                                                  94-96° C.                                       poxy]quinoline                                                        283     7-chloro-N-[2-(4-chlorophenyl)-                                                                      145-147° C.                                     propyl]-4-quinolinamine                                               284     4-[(4,5-dibromopentyl)oxy]-8-fluoro-                                                                 70-73° C.                                       quinoline                                                             285     8-fluoro-4-[(8-phenoxyoctyl)oxy]-                                                                    80-81° C.                                       quinoline                                                             286     6-chloro-2-methyl-4-[2-[4-( .sub.- t-butyl)-                                                         83-86° C.                                       phenyl]ethoxy]quinoline                                               287     8-fluoro-4-[(6-phenoxyhexyl)oxy]-                                                                    NA                                                     quinoline                                                             288     8-chloro-N-(2-methyl-2-phenylpropyl)-                                                                137-139° C.                                     4-quinolinamine                                                       289     8-fluoro-N-(2-methyl-2-phenylpropyl)-                                                                136-138° C.                                     4-quinolinamine                                                       290     6-methoxy-2-methyl-N-[2-(3-phenoxy-                                                                  NA                                                     phenyl)ethyl]-4-quinolinamine                                         291     8-fluoro-N-[2-[4-(phenylmethoxy)-                                                                    157-159° C.                                     phenyl]ethyl]-4-quinolinamine                                         292     7-fluoro-4-[2-(4-bromophenoxy)-                                                                      127-129° C.                                     ethoxy]quinoline                                                      293     N-[2-(4-hydroxyphenyl)ethyl]-8-                                                                      249-251° C.                                     fluoro-4-quinoline                                                    294     8-fluoro-4-[3-[3-(trifluoromethyl)-                                                                  67-69° C.                                       phenyl]propoxy]quinoline                                              295     8-fluoro-4-(2-phenylcyclohexyloxy)-                                                                  NA                                                     quinoline                                                             296     8-chloro-N-[2-(2,4-difluorophenyl)-                                                                  206-208° C.                                     ethyl]-4-quinolinamine                                                297     8-fluoro-4-[2-[4-(1,1,2,2-tetra-                                                                     70-72° C.                                       fluoroethoxy)phenyl]ethoxy]quinoline                                  298     N-[2-[3,4-bis(phenylmethoxy)-                                                                        137-139° C.                                     phenyl]ethyl]-8-fluoro-4-quinolinamine                                299     4-[2-(6-chloro-1,3-benzodioxol-5-yl)-                                                                143-145° C.                                     ethoxy]-8-fluoroquinoline                                             300     8-fluoro-N-[2-(4-ethoxyphenyl)ethyl]-                                                                179-181° C.                                     4-quinolinamine                                                       301     N-[2-(4-ethoxyphenyl)ethyl]-4-                                                                       125-126° C.                                     quinolinamine                                                         302     8-fluoro-4-[3-(4-ethoxyphenyl)propyl]-                                                               oil                                                    quinoline                                                             303     4-[3-(4-ethoxyphenyl)propyl]quinoline                                                                oil                                            304     8-fluoro-4-[3-(4-methoxyphenyl)-                                                                     oil                                                    propyl]quinoline                                                      305     8-fluoro-4-(2,2-dimethylbutoxy)-                                                                     oil                                                    quinoline                                                             306     8-fluoro-N-[2-[4-(butoxy)phenyl]-                                                                    118-120° C.                                     ethyl]-4-quinolinamine                                                307     7-[(8-fluoro-4-quinolinyl)oxy]-                                                                      94-96° C.                                       heptanenitrile                                                        308     8-fluoro-4-[2-(3,4-difluorophenyl)-                                                                  87-89° C.                                       ethoxy]quinoline                                                      309     8-fluoro-4-[2-(1,3-benzodioxol-5-                                                                    103-105° C.                                     yl)ethoxy]quinoline                                                   310     4-[2-(2,6-dichlorophenyl)ethoxy]-                                                                    128-129° C.                                     8-fluoroquinoline                                                     311     8-chloro-4-[2-(2-chloro-4-fluoro-                                                                    104-106° C.                                     phenyl)ethoxy]quinoline                                               312     8-fluoro-N-[2-(3-methoxyphenyl)-                                                                     153-155° C.                                     ethyl]-4-quinolinamine                                                313     8-fluoro-N-[2-(4-ethylphenyl)-                                                                       162-164° C.                                     ethyl]-4-quinolinamine                                                314     8-fluoro-4-[2-[4-(heptyloxy)phenyl]-                                                                 45-47° C.                                       ethoxy]quinoline                                                      315     (E)-8-fluoro-4-[(2-phenylethenyl)-                                                                   99-101° C.                                      oxy]quinoline                                                         316     (Z)-8-fluoro-4-[(2-phenylethenyl)-                                                                   95-97° C.                                       oxy]quinoline                                                         317     8-fluoro-N-[2-[4-(propoxy)phenyl]-                                                                   140-142° C.                                     ethyl]-4-quinolinamine                                                318     8-chloro-4-[2-(3,4-difluorophenyl)-                                                                  84-86° C.                                       ethoxy]quinoline                                                      319     4-[3-[4-( .sub.- i-propyl)phenyl]propyl]-                                                            oil                                                    quinoline                                                             320     7-chloro-4-[2-(1,3-benzodioxol-5-yl)-                                                                75-77° C.                                       ethoxy]quinoline                                                      321     8-fluoro-4-[2-(4-methoxyphenoxy)-                                                                    107-109°  C.                                    ethoxy]quinoline                                                      322     8-fluoro-4-[2-[4-(3-methylphenoxy)-                                                                  98-100° C.                                      phenyl]ethoxy]quinoline                                               323     8-chloro-4-[2-(2,4-difluorophenyl)-                                                                  118-120° C.                                     ethoxy]quinoline                                                      324     N-[2-(5-bromo-2-methoxyphenyl)ethyl]-                                                                176-178° C.                                     8-fluoro-4-quinolinamine                                              325     8-fluoro-4-[2-(4-propoxyphenyl)-                                                                     108-110° C.                                     ethoxy]quinoline                                                      326     8-fluoro-4-(2-phenoxyethoxy)quinoline                                                                118-120° C.                             327     8-fluoro-N-[4-[4-(trifluoromethyl)-                                                                  110-112° C.                                     phenyl]butyl]-4-quinolinamine                                         328     8-fluoro-N-[2-[4-(1,1,2,2-tetra-                                                                     168-170° C.                                     fluoroethoxy)phenyl]ethyl]-4-quinolin-                                        amine                                                                 ______________________________________                                    

The procedures described in the following detailed Examples arerepresentative of the procedures used to prepare the compounds of theother Examples.

EXAMPLE 4

N-Ethyl-N-(2-phenylethyl)-4-quinolinamine

To a suspension of 0.59 g of lithium aluminum hydride in 100 mL of dryether was added, dropwise, a solution of 2.3 g ofN-(2-phenylethyl)-N-(4-quinolinyl)acetamide dissolved in 50 mL of dryether. The mixture was heated to reflux for seven hours. Excess lithiumaluminum hydride was then destroyed by adding 100 mL of water to themixture. The solvent was then removed, and the residue was dissolved inchloroform. After washing with water, the mixture was then dried andconcentrated. Using HPLC (silica gel, CH₂ Cl₂ →EtOAc), 0.80 g of thetitle product was isolated. Yield 36.7%. M.P. oil.

EXAMPLE 10 N-[2-(4-Chlorophenyl)ethyl]-N-[8-fluoro-4quinolinyl]acetamide

A mixture of 2.0 g ofN-[2-(4-chlorophenyl)ethyl]-8-fluoro-4-quinolinamine and 5.0 mL ofacetic anhydride was refluxed overnight. The mixture was then cooled,and solvents were removed by reducing pressure. The residue was washedwith water and then dried. The resulting oil was passed over a silicagel column with ethyl acetate, and the front running spot was collected,producing 0.8 g of the title product as a thick oil.

EXAMPLE 25 2-Chloro-N-(2-phenylethyl)-4-quinolinamine

To 0.6 g of 2-hydroxy-N-(2-phenylethyl)-4-quinolinamine was added 15 mLof POCl₃. The mixture was heated to reflux overnight, then cooled andconcentrated to dryness. A mixture of ammonium hydroxide in water wasadded, then the product was extracted into CH₂ Cl₂. This solution wasconcentrated to dryness, and the product was recrystallized frompentane/CH₂ Cl₂, giving 0.55 g of the title product. Yield 85.9%. M.P.132°-133° C.

EXAMPLE 69 3-Chloro-N-(2-chloro-2-phenylethyl)-4-quinolinamine

A mixture of 4.1 g of 1-phenyl-2-(4-quinolinylamino)ethanol, 100 mL ofPOCla and 6.5 g of PCls was heated to reflux for 18 hours, then cooledand concentrated to dryness. An ice/water mixture was added, then theproduct was extracted into CH₂ Cl₂. This solution was concentrated todryness, and the residue was purified by HPLC (silica gel column elutedwith pentane/CH₂ Cl₂ (50:50)). Fractions containing the product werecombined and concentrated to dryness producing 0.433 g of the titleproduct. Yield 8.7%. M.P. oil.

EXAMPLE 97 8-Fluoro-N-[2-(2-trifluoromethyl)phenyl]-4-quinolinamine

To 2.0 g of 4-chloro-8-fluoroquinoline was added 4.1 g of2-[2-(trifluoromethyl)phenyl]ethylamine. The mixture was stirred andheated to 160°-165° C. under nitrogen for two hours, then cooled, and200 mL of a 50:50 mixture of ammonium hydroxide and water was added. Theproduct was extracted into CH₂ Cl₂, which was concentrated to dryness.Recrystallization from a pentane/CH₂ Cl₂ mixture yielded 1.5 g of thetitle product. Yield 41.6%.

EXAMPLE 154 8-Fluoro-N-[2-(4-phenyl-2-thiazolyl)ethyl]-4-quinolinamine

To 1.0 g of 4-chloro-8-fluoroquinoline was added 2.6 g of2-β-aminoethyl-4-phenylthiazole monohydrochloride. The mixture wasstirred under nitrogen and heated to 170°-175° C. for one hour. Themixture was then cooled and 250 mL of a 50:50 mixture of ammoniumhydroxide and water was added. The product was extracted into CH₂ Cl₂,which was then concentrated to dryness. Recrystallizing from pentane/CH₂Cl₂ gave 0.410 g of the title product. Yield 21.6%. M.P. 134°-135° C.

EXAMPLE 159 8-Fluoro-N-[2-(2-naphthyl)ethyl]-4-quinolinamine

A mixture of 2.0 g of 4-chloro-8-fluoroquinoline and 3.8 g of2-(2-naphthyl)ethyl amine was heated under nitrogen to 160°-165° C. forone hour. Then 200 mL of a 50:50 mixture of ammonium hydroxide in waterwas added. The product was extracted from the mixture into CH₂ Cl₂,which was then concentrated to dryness. The residue was recrystallizedfrom pentane/ethyl acetate to give 1.4 g of the title product. Yield41.2%. M.P. 173°-174° C.

EXAMPLE 173 8-Fluoro-N-[2-(2-thienyl)ethyl]-4-quinolinamine

A mixture of 2.0 g of 4-chloro-8-fluoroquinoline and 2.8 g of2-(2-thienyl)ethyl amine was heated under nitrogen to 160°-165° C. fortwo hours, then cooled and combined with 200 mL of a 50:50 mixture ofammonium hydroxide and water. The product was extracted into CH₂ Cl₂,which was then concentrated to dryness. The residue was recrystallizedfrom pentane/CH₂ Cl₂ to give 1.0 g of the title product. Yield 34.5%.M.P. 157°-158° C.

EXAMPLE 181 Bis[2-phenylethyl]-2,4-quinolinediamine

To 2.0 g of 2,4-dichloroquinoline was added 4.8 g of 2-phenylethylamine,and the mixture was heated to 150°-160° C. under nitrogen for 18 hours.The mixture was then cooled and a solution of ammonium hydroxide andwater was added. The product was extracted into CH₂ Cl₂, which was thenconcentrated to dryness, giving an oil. To the oil, 100 mL of pentaneand CH₂ Cl₂ was added and the oil went into solution. This solution wascooled, and the title product crystallized. Yield 44.4%. M.P. 70°-71° C.

EXAMPLE 186 N,N'-Bis[2-(4-chlorophenyl)ethyl]-2,7-quinolinediamine

A mixture of 2.0 g of 4-chloro-7-fluoroquinoline and 3.5 g of2-(4-chlorophenyl)ethyl amine was heated neat until fuming began. Themixture was then cooled. The product was extracted into a CHClz/ammoniumhydroxide solution, which was then washed with water. Solvent wasremoved by reducing pressure. The residue was placed on a silica gelcolumn with acetone, then flushed with ethanol. Solvent was removed byreducing pressure, giving the title product as a yellow-brown foam.Yield 1.1 g. M.P. 55°-60° C.

EXAMPLE 209 4-[2-(4-Chlorophenyl)ethoxy]-8-fluoroquinoline

To 1.2 g of sodium hydride in 50 mL of DMF was added 3.9 g of2-(4-chlorophenyl)ethyl alcohol. The mixture was stirred at roomtemperature for one hour, then 4.5 g of 4-chloro-8-fluoroquinoline in 10mL of DMF was added, the mixture was heated to reflux for two hours.Then the mixture was allowed to cool to room temperature while it wasstirred for four hours, after which it was poured into an ice/watermixture. The mixture was filtered, and the filter cake was washed withH₂ O. Recrystallization from pentane/ethyl acetate gave 0.840 g of thetitle product. Yield 11.2%. M.P. 139°-140° C.

EXAMPLE 221 4-[2-[4-(t-Butyl)phenyl]ethoxy]-8-fluoroquinoline

To a mixture of 1.1 g of sodium hydride in 50 mL of DMF was added 4.0 gof 2-[4-(1,1-dimethylethyl)phenyl]ethyl alcohol, and the mixture wasstirred for one hour at room temperature. Then 4.0 g of4-chloro-8fluoroquinoline in 20 mL of DMF were added, and the mixturewas stirred at room temperature overnight. Then the mixture was pouredinto an ice/water mixture, and the solid was collected andrecrystallized from ethyl acetate/pentane to give 2.3 g of the titleproduct. Yield 32.4%. M.P. 81°-82° C.

EXAMPLE 238 8-Fluoro-4-[2-[4-(i-propyl)phenyl]ethoxyquinoline

To a suspension of 0.96 g of sodium hydride in 10 mL of dry DMF wasadded 3.6 g of 4-chloro-8-fluoroquinoline. The mixture was cooled in anice/water bath, and 3.3 g of 2-[4-(1-methylethyl)phenyl]ethyl alcoholwas added. The mixture was stirred overnight, then diluted with ice andwater. The pH was adjusted to 7, then the product was extracted into CH₂Cl₂. The CH₂ Cl₂ layer was separated, filtered, and evaporated in vacuo.An azeotrope with xylene was formed to facilitate removal of residualDMF. The residue was chromatographically purified on a silica gelcolumn, eluting with CH₂ Cl₂, →5% EtOAc/CH₂ Cl₂ →10% EtOAc/CH₂ Cl₂. Thefractions containing product were combined and evaporated to give anoil, which crystallized on adding ether. Recrystallization yielded 2.5 gof title product. M.P. 56°-60° C.

EXAMPLES 212 and 251 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline,4,8-Bis[2-(4-methylphenyl)ethoxy]quinoline

To a solution of 1.2 g of sodium hydride in 50 ml of DMF was added 3.4 gof 2-(4-methylphenyl)ethanol, and the mixture was stirred for one hourat room temperature. Then 4.5 g of 4-chloro-8-fluoroquinoline wereadded, the mixture was heated to reflux for five hours, and then cooledto room temperature, and poured into a mixture of ice in water. Thesolid phase was collected and dried. TLC showed three products. Thesewere separated by HPLC (silica gel, 70% pentane/30% EtOAc) giving 1.84 gof 8-fluoro-4-[2-(4-methylphenyl)ethoxy]quinoline (Yield: 26.3%; M.P.89°-90° C.) 0.610 g of 4-chloro-8-[2-(4-methylphenyl)ethoxy]quinoline(Yield: 8.7%; M.P. 74°-75° C.); and 0.450 g of4,8-bis[2-(4-methylphenyl)ethoxy]quinoline (Yield: 6.4%; M.P. 142°-143°C).

EXAMPLE 261 4-[3-(4-chlorophenyl)propyl]-8-fluoroquinoline

A mixture of 3.63 g of 4-chloroquinoline and 5.3 g of5-[2-(4-chlorophenyl)ethyl]barbituric acid was heated to 150° C. for11/4 hours, to form5-[2-(4-chlorophenyl)ethyl]-5-(4-quinolinyl)barbituric acid. Thiscompound was hydrolyzed, without isolation, by adding 4 g of NaOH in 40ml of water and refluxing for four hours. The mixture was cooled,acidified with HCl and refluxed for several hours, cooled, andneutralized with dilute NaOH. The desired product was extracted into CH₂Cl₂, which was then filtered through phase separating paper andevaporated to dryness. The residue was absorbed onto silica gel andchromatographed over silica gel using CH₂ Cl₂. Fractions containingproduct were combined to give 2.69 g of crystalline material. This wasrecrystallized from a petroleum ether/CH₂ Cl₂ mixture to give 2.35 g ofthe title product. Yield: 39%. M.P. 97° C.

Utility Plant Pathology

The compounds of the present invention have been found to control fungi,particularly plant pathogens. When employed in the treatment of plantfungal diseases, the compounds are applied to the plants in a diseaseinhibiting and "phytologically acceptable amount". The term "diseaseinhibiting" and "phytologically acceptable amount," as used herein,refers to an amount of a compound of the invention which kills orinhibits the plant disease for which control is desired, but is notsignificantly toxic to the plant. This amount will generally be fromabout 1 to 1000 ppm, with 10 to 500 ppm being preferred. The exactconcentration of compound required varies with the fungal disease to becontrolled, the type formulation employed, the method of application,the particular plant species, climate conditions and the like. Thecompounds of the invention may also be used to protect stored grain andother non-plant loci from fungal infestation.

Greenhouse Tests

The following experiments were performed in the laboratory, to determinethe fungicidal efficacy of the compounds of the invention.

Test 1

This screen was used to evaluate the efficacy of the present compoundsagainst a variety of different organisms that cause plant diseases.

The test compounds were formulated for application by dissolving 50 mgof the compound into 1.25 ml of solvent. The solvent was prepared bymixing 50 ml of "Tween 20" with 475 ml of acetone and 475 ml of ethanol.The solvent/compound solution was diluted to 125 ml with deionizedwater. The resulting formulation contains 400 ppm test chemical. Lowerconcentrations were obtained by serial dilution with thesolvent-surfactant mixture.

The formulated test compounds were applied by foliar spray. Thefollowing plant pathogens and their corresponding plants were employed.

    ______________________________________                                                        Designation in                                                Pathogen        Following Tables                                                                           Host                                             ______________________________________                                        Erysiphe graminis tritici                                                                     POWD         wheat                                            (powdery mildew)                                                                              MDEW                                                          Pyricularia oryzae                                                                            RICE         rice                                             (rice blast)    BLAS                                                          Puccinia recondita tritici                                                                    LEAF         wheat                                            (leaf rust)     RUST                                                          Botrytis cinerea                                                                              GRAY         grape berries                                    (gray mold)     MOLD                                                          Pseudoperonospora cubensis                                                                    DOWN         squash                                           (downy mildew)  MDEW                                                          Cercospora beticola                                                                           LEAF         sugar beet                                       (leaf spot)     SPOT                                                          Venturia inaequalis                                                                           APPL         apple seedling                                   (apple scab)    SCAB                                                          Septoria tritici                                                                              LEAF         wheat                                            (leaf blotch)   BLOT                                                          ______________________________________                                    

The formulated technical compounds were sprayed on all foliar surfacesof the host plants (or cut berry) to past run-off. Single pots of eachhost plant were placed on raised, revolving pedestals in a fume hood.Test solutions were sprayed on all foliar surfaces. All treatments wereallowed to dry and the plants were inoculated with the appropriatepathogens within 2-4 hours.

The effectiveness of test compounds in controlling disease was rated onthe following scale:

    ______________________________________                                        0 =          not tested against specific organism                             - =          0-19% control at 400 ppm                                         + =          20-89% control at 400 ppm                                        ++ =         90-100% control at 400 ppm                                       +++ =        90-100% control at 400 ppm.                                      ______________________________________                                    

Table 13 gives the results.

                                      TABLE 13                                    __________________________________________________________________________    EX. POWD RICE LEAF GRAY DOWN LEAF APPL LEAF                                   NO. MDEW BLAST                                                                              RUST MOLD MDEW SPOT SCAB BLOT                                   __________________________________________________________________________    1   +    +    +    +    ++   0    -    -                                      2   -    -    -    -    +++  0    -    -                                      3   -    ++   +    -    +++  0    -    -                                      4   +    +    ++   -    ++   0    -    -                                      5   ++   ++   +++  -    +++  0    -    +++                                    6   ++   +    +    +    ++   0    -    -                                      7   +    +    +++  -    +++  -    -    +++                                    8   +    ++   +    -    +++  +++  -    +                                      9   +    +    +    -    +++  -    -    -                                      10  ++   +++  +++  -    ++   +++  -    +++                                    11  -    ++   +++  -    ++   +++  -    -                                      12  +    ++   +++  -    ++   +++  -    ++                                     13  -    ++   ++   -    ++   -    -    -                                      14  -    +    +    -    +++  +++  -    -                                      15  -    +    +    -    +++  +++  +    -                                      16  -    +    +    -    +++  +++  -    -                                      17  ++   +    ++   -    ++   0    -    -                                      18  +    ++   ++   +    ++   0    -    -                                      19  +    ++   ++   -    +++  0    -    -                                      20  +    +    +    -    +++  0    -    -                                      21  +    +    +    -    ++   0    -    -                                      22  +    +    +    -    +++  0    -    -                                      23  +    +    +    -    +++  0    -    -                                      24  +    +    +    -    +++  0    -    -                                      25  +    +    ++   -    +++  0    -    -                                      26  +    +    -    -    +++  0    -    -                                      27  +    ++   +    -    +++  0    -    -                                      28  +    ++   +    -    +++  0    -    -                                      29  -    +    +    -    -    0    0    0                                      30  -    +    +    -    +++  0    -    -                                      31  ++   +    +    -    +++  0    -    -                                      32  +    +    -    -    +++  0    -    -                                      33  -    +    +    -    +++  0    -    -                                      34  +    +    ++   -    +++  +    -    -                                      35  +    +    +    -    +++  +++  -    -                                      36  +    +++  +++  -    +++  +++  -    +++                                    37  +    -    +    -    +    0    0    0                                      38  +    -    ++   -    +++  +    -    -                                      39  +++  +++  +++  -    +++  0    0    0                                      40  -    ++   +++  -    +    0    0    0                                      41  +    ++   +++  -    ++   +++  -    +                                      42  +++  +    ++   -    +++  +++  -    -                                      43  +    +    -    -    ++   +++  -    -                                      44  +++  +    +    -    +++  +++  +    -                                      45  +    ++   +    -    ++   +++  -    -                                      46  +    ++   +    -    ++   +++  +    +                                      47  +    -    +    -    +    0    0    0                                      48  +    +    +    -    ++   +    -    -                                      49  -    +    +    -    +    0    0    0                                      50  +++  -    ++   -    +++  -    -    -                                      51  -    +    +    -    +++  +++  -    -                                      52  -    +    +    -    +++  +    -    +++                                    53  +++  +    +    -    +++  +++  -    +                                      54  -    ++   +    -    +++  +++  -    +                                      55  +    ++   +    -    ++   +++  -    -                                      56  -    ++   ++   -    +++  +++  -    +                                      57  -    ++   +    -    ++   +++  -    -                                      58  -    -    +    -    +++  0    0    0                                      59  +    +    -    -    -    0    0    0                                      60  ++   +++  ++   -    +++  0    0    0                                      61  -    ++   ++   -    +++  0    0    0                                      62  -    ++   ++   -    +++  -    -    +                                      63  -    +    +++  -    ++   0    0    0                                      64  +    -    +    -    +++  0    0    0                                      65  +    +    ++   -    +++  -    -    +                                      66  +    ++   +++  -    +++  +++  -    +                                      67  -    +    +    -    ++   +    -    -                                      68  +    +    +++  -    ++   -    -    +++                                    69  +    +    +    -    +++  -    -    -                                      70  + ++ +    +    -    -    -    -    -                                      71  +    +    +++  -    +++  +++  -    +                                      72  ++   +++  +++  -    +++  0    0    0                                      73  -    +    -    -    ++   -    -    -                                      74  +    +    +++  -    +++  +++  -    -                                      75  +    +    ++   -    +++  -    -    +                                      76  ++   +++  +++  -    +++  -    +    +++                                    77  +    +    ++   -    +++  -    +    -                                      78  +    ++   +++  -    +++  +++  -    +                                      79  +    ++   ++   -    ++ + +++  -    +                                      80  +    ++   ++   -    +++  +    -    -                                      81  +    ++   ++   -    +++  +    -    -                                      82  +    +++  +++  -    +++  +    -    +++                                    83  +    ++   +++  +++  ++   +    -    -                                      84  +++  ++   ++   -    ++   +    -    -                                      85  -    -    +    -    -    0    0    0                                      86  -    -    +    -    +    0    0    0                                      87  -    -    +    -    +++  -    -    -                                      88  -    -    ++   -    ++   +    -    -                                      89  -    -    +    -    +++  0    0    0                                      90  -    +++  +++  -    +++  0    0    0                                      91  +    +    -    -    ++   -    -    -                                      92  +    ++   +++  -    ++   +    -    +++                                    93  -    -    -    -    -    +    -    +                                      94  +    +++  +++  -    +++  +++  -    +                                      95  +    ++   +++  +    +++  +    +    +++                                    96  +    +++  +++  -    +++  +++  -    +++                                    97  +    +++  +++  -    +++  +++  -    +++                                    98  -    +    ++   -    ++   -    -    -                                      99  -    ++   +++  -    +++  +    -    -                                      100 +    +    +    -    +    0    0    0                                      101 +++  -    +    -    +++  +++  +    -                                      102 +    +    -    -    -    0    0    0                                      103 +    ++   ++   -    +++  +    +++  +                                      104 -    -    -    -    ++   +    +    -                                      105 +++  ++   +++  -    +++  +    -    +                                      106 ++   +    +    -    +    +    -    +                                      107 ++   +    +    -    +++  -    -    -                                      108 +    +    ++   -    +    -    -    +++                                    109 +    +    ++   -    +++  0    0    0                                      110 -    +    ++   -    ++   0    0    0                                      111 +    ++   +++  -    +++  -    -    +++                                    112 -    -    +    -    +++  -    -    -                                      113 +    +++  +++  -    +++  -    -    +++                                    114 +++  +++  +++  -    +++  +++  -    +++                                    115 -    +    -    -    +    0    0    0                                      116 -    +    +++  -    +++  +    +    -                                      117 +    +    +    -    +++  +    -    -                                      118 -    +    -    -    -    -    -    -                                      119 +    +    +    -    ++   -    +    +                                      120 -    +    +    -    ++   +++  -    -                                      121 +    -    ++   -    +    0    0    0                                      122 -    ++   +    -    ++   -    -    -                                      123 -    +    +    -    +++  -    -    -                                      124 +++  +    +    -    -    -    -    -                                      125 +    -    -    -    -    0    0    0                                      126 ++   +++  +    -    +    -    -    +                                      127 +    +    +    -    +    0    0    0                                      128 -    +    +    -    -    0    0    0                                      129 -    +    ++   -    +    -    +    -                                      130 -    -    -    -    -    0    0    0                                      131 -    -    -    -    +    0    0    0                                      132 -    -    -    -    -    0    0    0                                      133 -    +    +    -    +    0    0    0                                      134 +    ++   +    -    +++  0    0    0                                      135 -    -    -    -    +++  -    -    +                                      136 +    -    -    -    +++  -    -    -                                      137 +    +++  +    -    +++  0    0    0                                      138 -    +    +    -    +++  0    0    0                                      139 +    +    +    -    ++   -    -    -                                      140 +    +++  +++  -    +++  +++  +    +++                                    141 -    ++   +    -    +    0    0    0                                      142 -    ++   ++   -    +++  0    0    0                                      143 ++   ++   + ++ -    +++  +    -    +                                      144 -    +    ++   -    +++  +    +    -                                      145 -    +    +    -    +++  +    -    -                                      146 -    -    -    -    +    0    0    0                                      147 -    +    +    -    +++  -    -    -                                      148 -    +    +    -    ++   +    -    -                                      149 +    +    ++   -    ++   +++  -    +                                      150 +    +    ++   -    ++   +++  -    +++                                    151 +    +    ++   -    +++  +    -    +                                      152 ++   +++  ++   -    +++  +++  -    +++                                    153 +    ++   ++   -    +    -    -    -                                      154 ++   +    +++  -    +++  +    +    +                                      155 -    +    -    -    +++  -    -    -                                      156 -    +    +    -    +++  -    -    -                                      157 -    ++   ++   -    +++  0    0    0                                      158 +    +++  +++  -    +++  +    -    +++                                    159 ++   +++  +++  -    +++  +    -    +++                                    160 -    +    -    -    -    0    0    0                                      161 +    +    -    -    +    0    0    0                                      162 +    +    ++   -    +++  -    -    -                                      163 ++   +    +++  -    ++   +++  -    -                                      164 -    +    +    +    ++   +    -    -                                      165 +    ++   ++   -    +++  +++  +    -                                      166 +    +    +    -    +++  -    -    +                                      167 +    -    -    -    +    0    0    0                                      168 +    ++   ++   -    +++  -    -    -                                      169 +    ++   +    -    ++   -    -    -                                      170 +    +    ++   -    +    -    -    -                                      171 -    +    +    -    +    +    -    +                                      172 +    +    +    -    +    -    -    -                                      173 +    +    ++   -    +++  +++  -    +                                      174 +    +    ++   -    +++  -    -    +                                      175 +    +    +++  -    +++  -    -    +                                      176 +    +    +    -    ++   +    -    -                                      177 ++   +++  +++  -    +++  0    0    0                                      178 -    +    ++   -    +++  0    0    0                                      179 -    -    -    -    ++   +    +    -                                      180 ++   +    -    -    ++   +    -    +                                      181 +    +    +    -    +++  0    -    -                                      182 -    +    -    -    -    0    0    0                                      183 -    ++   ++   -    +++  +    +    -                                      184 -    +    ++   -    ++   -    -    -                                      185 -    +    +    -    +    0    0    0                                      186 -    -    +    -    +++  +    -    +                                      187 -    +    +    -    +++  -    -    -                                      188 -    ++   +    -    ++   0    0    0                                      189 -    +    +    -    +    -    -    -                                      190 -    +    +++  -    -    -    -    -                                      191 -    +    ++   -    -    0    0    0                                      192 -    -    ++   -    +++  -    -    +                                      193 -    -    +    -    -    0    0    0                                      194 +    -    -    -    -    0    0    0                                      195 +++  +++  +++  -    +++  0    0    0                                      196 +++  +++  +++  -    +++  0    0    0                                      197 +++  +++  +++  -    +    0    0    0                                      198 -    -    -    -    -    0    0    0                                      199 ++   ++   +++  -    +++  0    0    0                                      200 +++  +++  +++  -    +    +    +    +++                                    201 +++  +    +++  -    +++  +++  +    +++                                    202 +++  +    ++   -    ++   +    -    +                                      203 +    +++  +++  -    ++   +    +    ++                                     204 +    -    +    -    +    0    0    0                                      205 ++   +++  +++  -    +++  0    0    0                                      206 +++  +++  +++  -    +++  0    0    0                                      207 ++   +++  +++  -    +++  +    +    +++                                    208 ++   +++  +++  -    +++  +    -    +                                      209 +++  +++  +++  -    +++  +++  +    +++                                    210 ++   +++  +++  -    +++  +    -    +++                                    211 ++   +++  +++  -    +++  +++  -    +++                                    212 ++   +++  +++  -    +++  -    +++  +++                                    213 +    ++   ++   -    +++  -    +    +                                      214 +    +++  +    -    ++   0    0    0                                      215 -    +    +    -    ++   0    0    0                                      216 ++   ++   ++   -    ++   0    0    0                                      217 +++  +++  +++  -    +++  0    0    0                                      218 +++  +++  +++  -    +++  0    0    0                                      219 ++   +++  +++  -    +++  +    +    +                                      220 ++   +    ++   -    ++   -    +    -                                      221 +    -    +++  -    +++  +++  +    +++                                    222 +    +    +++  -    +++  +    +++  +++                                    223 ++   +++  +++  -    -    0    0    0                                      224 ++   +++  +++  -    +++  0    0    0                                      225 ++   +++  +++  -    +++  0    0    0                                      226 +    -    +    -    +    0    0    0                                      227 -    +    +    -    -    0    0    0                                      228 ++   +++  +++  -    +++  +    +++  +++                                    229 +    +++  ++   -    +++  -    -    +                                      230 ++   -    +    -    -    -    -    -                                      231 +    -    -    -    -    0    0    0                                      232 -    -    -    -    -    0    0    0                                      233 +    ++   ++   -    +    -    -    +                                      234 +    +    ++   -    +    +    -    +                                      235 +    ++   ++   -    +    -    -    +                                      236 +++  -    +    -    -    -    -    -                                      237 ++   ++   +    -    -    0    0    0                                      238 +++  +++  +++  +    ++   0    0    0                                      239 +++  ++   ++   -    ++   0    0    0                                      240 -    +    ++   -    -    0    0    0                                      241 -    -    -    -    -    0    0    0                                      242 -    -    -    -    -    0    0    0                                      243 -    -    -    -    -    0    0    0                                      244 +    ++   +    -    +    -    -    +                                      245 +    ++   ++   -    ++   -    -    -                                      246 ++   +++  +++  -    +++  +    +++  +++                                    247 ++   +++  +++  -    +    -    -    +++                                    248 +    -    -    -    -    0    0    0                                      249 -    -    -    -    -    0    0    0                                      250 -    -    +    -    +    0    0    0                                      251 -    +    -    -    +    -    -    -                                      252 ++   ++   +++  -    ++   -    +    +                                      253 +++  ++   +++  -    ++   +    +++  +                                      254 ++   ++   -    -    -    0    0    0                                      255 +    +++  +++  -    +    0    0    0                                      256 +++  +++  +++  -    ++   0    0    0                                      257 +++  +    +++  -    +++  0    0    0                                      258 ++   +++  ++   -    ++   +    -    +                                      259 +    +++  +++  +    +++  -    +++  +++                                    260 ++   +++  +++  -    +++  +    -    +++                                    261 +    +    +++  -    +    -    +    +                                      262 -    ++   +++  -    +++  0    0    0                                      263 +    +    +    -    -    0    0    0                                      264 -    -    +    -    0    0    0    0                                      265 -    ++   ++   -    -    0    0    0                                      266 -    -    -    -    -    0    0    0                                      267 ++   +++  ++   -    +    0    0    0                                      268 +    +++  +++  -    +++  0    0    0                                      269 ++   +++  +++  -    +++  0    0    0                                      270 -    +    -    -    -    0    0    0                                      271 -    +++  +    -    +++  0    0    0                                      272 -    +    -    -    +    0    0    0                                      273 +    ++   +    -    +    0    0    0                                      274 ++   ++   ++   -    +    0    0    0                                      275 +++  +++  +++  -    +++  0    0    0                                      276 +++  -    +    -    -    0    0    0                                      277 ++   -    -    -    -    0    0    0                                      278 +++  +++  +++  -    +++  0    0    0                                      279 -    ++   ++   -    ++   0    0    0                                      280 +++  +++  +++  -    +++  0    0    0                                      281 +    +++  +    -    ++ + 0    0    0                                      282 -    +    -    -    -    0    0    0                                      283 +    +    ++   -    ++   0    0    0                                      284 -    +++  ++   -    +    0    0    0                                      285 -    -    -    -    -    0    0    0                                      286 +    -    +    -    -    0    0    0                                      287 -    -    +    -    ++   0    0    0                                      288 -    +    -    -    +    0    0    0                                      289 +    ++   ++   -    +++  0    0    0                                      290 -    +++  +    -    +++  0    0    0                                      291 +++  +++  +++  -    +++  0    0    0                                      292 -    -    -    -    -    0    0    0                                      293 -    -    ++   -    -    0    0    0                                      294 -    -    -    -    -    0    0    0                                      295 +    +    +    -    ++   0    0    0                                      296 -    ++   ++   -    +    0    0    0                                      297 +++  ++   +++  -    +++  0    0    0                                      298 -    -    -    -    -    0    0    0                                      299 +    ++   +++  -    ++   0    0    0                                      300 +    +++  +++  -    +++  0    0    0                                      301 -    -    +++  -    +++  0    0    0                                      302 +++  +++  +++  -    +++  0    0    0                                      303 +++  +++  +++  -    +++  0    0    0                                      304 +    +++  +++  -    +++  0    0    0                                      305 +    +    -    -    +    0    0    0                                      306 +    +++  +++  -    +++  0    0    0                                      307 -    -    +    -    -    0    0    0                                      308 +    +++  +++  -    +++  0    0    0                                      309 +    +++  +++  -    +++  0    0    0                                      310 -    ++   -    -    -    0    0    0                                      311 +    -    ++   -    ++   0    0    0                                      312 ++   -    +++  -    +++  0    0    0                                      317 ++   +++  +++  -    +++  0    0    0                                      318 -    ++   ++   -    -    0    0    0                                      319 +++  +++  +++  -    ++   0    0    0                                      320 +    +    ++   -    +    0    0    0                                      321 -    +    ++   -    -    0    0    0                                      322 +++  +++  +++  -    +    0    0    0                                      323 +    ++   +++  -    -    0    0    0                                      324 -    -    +    -    +    0    0    0                                      325 ++   ++   +++  -    +++  0    0    0                                      326 -    +    +    -    -    0    0    0                                      327 +++  -    ++   -    +++  0    0    0                                      328 +    -    +++  -    +++  0    0    0                                      __________________________________________________________________________

Field Tests

Selected compounds were field tested against a variety of plantpathogens. The following table reports pathogens against which compoundsof the invention showed activity in these tests.

                  TABLE 14                                                        ______________________________________                                        COMPOUND                                                                      EX. NO.   CROP      PATHOGEN                                                  ______________________________________                                         2        barley    Pyrenophora teres                                                   potato    Phytophthora infestans                                              tomato    Phytophthora infestans                                     5        barley    Pyrenophora teres                                                             Rhynchosporium secalis                                              cucumber  Sphaerotheca fuliginea                                              grape     Plasmopara viticola                                                 potato    Phytophthora infestans                                              rape      Alternaria brassica                                                 tomato    Phytophthora infestans                                     10       barley    Rhynchosporium secalis                                                        Pyrenophora teres                                                             Erysiphe graminis hordei                                            cucumber  Sphaerotheca fuliginea                                              wheat     Pseudocercosporella                                                           herpotrichoides                                                               Erysiphe graminis tritici                                  97       grape     Plasmopara viticola                                       159       barley    Rhynchosporium secalis                                              grape     Plasmopara viticola                                                 wheat     Puccinia recondita                                        173       grape     Plasmopara viticola                                       200       barley    Rhynchosporium secalis                                                        Pyrenophora teres                                                             Erysiphe graminis hordei                                            cucumber  Sphaerotheca fuliginea                                              wheat     Pseudocercosporella                                                           herpotrichoides                                                               Erysiphe graminis tritici                                 212       apple     Podosphaera leucotricha                                             barley    Pyrenophora teres                                                   grape     Uncinula necator                                                              Plasmopara viticola                                                 rape      Alternaria brassica                                                 rice      Piricularia oryzae                                        212       barley    Rhynchosporium secalis                                                        Pyrenophora teres                                                             Erysiphe graminis hordei                                            cucumber  Sphaerotheca fuliginea                                              wheat     Pseudocercosporella                                                           herpotrichoides                                                               Erysiphe graminis tritici                                 219       barley    Rhynchosporium secalis                                                        Pyrenophora teres                                                             Erysiphe graminis hordei                                            cucumber  Sphaerotheca fuliginea                                              wheat     Pseudocercosporella                                                           herpotrichoides                                                               Erysiphe graminis tritici                                 221       sugar beet                                                                              Erysiphe sp.                                              ______________________________________                                    

Combinations

Fungal disease pathogens are known to develop resistance to fungicides.When strains resistant to a fungicide do develop, it becomes necessaryto apply larger and larger amounts of the fungicide to obtain desiredresults. To retard the development of resistance to new fungicides, itis desirable to apply the new fungicides in combination with otherfungicides. Use of a combination product also permits the product'sspectrum of activity to be adjusted.

Accordingly, another aspect of the invention is a fungicidal combinationcomprising at least 1% by weight of a compound of formula (1) incombination with a second fungicide.

Contemplated classes of fungicides from which the second fungicide maybe selected include:

(1) N-substituted azoles, for example propiconazole, triademefon,flusilazol, diniconazole, ethyltrianol, myclobutanil, and prochloraz;

(2) pyrimidines, such as fenarimol and nuarimol;

(3) morpholines, such as fenpropimorph and tridemorph;

(4) piperazines, such as triforine; and

(5) pyridines, such as pyrifenox. Fungicides in these five classes allfunction by inhibiting sterol biosynthesis. Additional classes ofcontemplated fungicides, which have other mechanisms of action, include:

(6) dithiocarbamates, such as maneb and mancozeb;

(7) phthalimides, such as captafol;

8) isophthalonitrites, such as chlorothalonil;

(9) dicarboximides, such as iprodione;

(10) benzimidazoles, such as benomyl and carbendazim;

(11) 2-aminopyrimidines, such as ethirimol;

(12) carboxamides, such as carboxin; and

(13) dinitrophenols, such as dinocap.

The fungicide combinations of the invention contain at least 1%,ordinarily 20 to 80%, and more typically 50 to 75% by weight of acompound of formula (1).

Combination Tests

Selected compounds were tested in the greenhouse in combination withother known fungicides against various plant pathogens. Results arereported in Tables 15 and 16. In the tables, the time given under "Timein hours" is the number of hours elapsing between treatment andinoculation. A negative time indicates that the pathogen was inoculatedbefore treatment. In such cases, curative activity was being tested. Apositive time indicates that the plants were treated before they wereinoculated with pathogen. In such cases, residual or protectant activitywas tested. The compounds were formulated and applied as foliar spraysas in Test 1. The results were evaluated on a 1-9 rating scale. Theseratings represent the following percent disease control:

1=0-19%, 2=20-29%, 3=30-39%, 4=40-59%, 5

6=75-89%, 7=90-96%, 8=97-99%, and 9=100%.

                  TABLE 15                                                        ______________________________________                                        CUCURBIT DOWNY MILDEW                                                         COMPOUND 1 TIME     RATE     RATE                                             PLUS       IN       CMPD 1   CMPD 2                                           COMPOUND 2 HOURS    IN PPM   IN PPM RESULTS                                   ______________________________________                                        Ex. 5      4        48.00           8.0                                                           24.00           7.5                                                           12.00           7.0                                                           6.00            1.0                                       nuarimol   4        2.00            1.0                                                           1.00            1.0                                                           0.50            1.0                                                           0.25            1.0                                       nuarimol + Ex. 5                                                                         4        2.00     48.00  8.5                                                           1.00     24.00  7.5                                                           0.50     12.00  5.0                                                           0.25      6.00  1.0                                       ______________________________________                                    

                  TABLE 16                                                        ______________________________________                                        CUCURBIT POWDERY MILDEW                                                       Ex. 5      4        48.00           6.0                                                           24.00           5.0                                                           12.00           1.0                                                           6.00            1.0                                       nuarimol   4        2.00            9.0                                                           1.00            8.0                                                           0.50            7.0                                                           0.25            6.0                                       nuarimol + Ex. 5                                                                         4        2.00     48.00  9.0                                                           1.00     24.00  9.0                                                           0.50     12.00  8.0                                                           0.25      6.00  6.0                                       ______________________________________                                    

Insecticide and Miticide Utility

The compounds of the invention are also useful for the control ofinsects and mites. Therefore, the present invention also is directed toa method for inhibiting an insect or mite which comprises applying to alocus of the insect or mite an insect- or mite-inhibiting amount of acompound of formula (1).

The compounds of the invention show activity against a number of insectsand mites. More specifically, the compounds show activity against melonaphid, which is a member of the insect order Homoptera. Other members ofthe Homoptera include leafhoppers, planthoppers, pear pyslla, applesucker, scale insects, whiteflies, spittle bugs as well as numerousother host specific aphid species. Activity has also been observedagainst greenhouse thrips, which are members of the order Thysanoptera.The compounds also show activity against Southern armyworm, which is amember of the insect order Lepidoptera. Other typical members of thisorder are codling moth, cutworm, clothes moth, Indianmeal moth, leafrollers, corn earworm, European corn borer, cabbage worm, cabbagelooper, cotton bollworm, bagworm, eastern tent caterpillar, sod webworm,and fall armyworm.

Representative mite species with which it is contemplated that thepresent invention can be practiced include those listed below.

    __________________________________________________________________________    FAMILY      SCIENTIFIC NAME                                                                              COMMON NAME                                        __________________________________________________________________________    ACARIDAE                                                                                  Aleurobius farinae                                                            Rhizoglyphus echinopus                                                                       Bulb mite                                                      Rhizoglyphus elongatus                                                        Rhizoglyphus rhizophagus                                                      Rhizoglyphus sagittatae                                                       Rhizoglyphus tarsalis                                             ERIOPHYIDAE                                                                               Abacarus farinae                                                                             Grain rust mite                                                Aceria brachytarsus                                                           Acalitus essigi                                                                              Redberry mite                                                  Aceria ficus                                                                  Aceria fraaxinivorus                                                          Aceria granati                                                                Aceria parapopuli                                                             Eriophyes sheldoni                                                                           Citrus bud mite                                                Aceria tulipae                                                                Aculus carnutus                                                                              Peach silver mite                                              Aculus schlechtendali                                                                        Apple rust mite                                                Colomerus vitis                                                                              Grape erineum mite                                             Eriophyes convolvens                                                          Eriophyes insidiosus                                                          Eriophyes malifoliae                                                          Eriophyes padi                                                                Eriophyes pruni                                                               Epitrimerus pyri                                                                             Pear leaf blister mite                                         Eriophyes ramosus                                                             Eriophyes sheldoni                                                                           Citrus bud mite                                                Eriophyes ribis                                                               Phyllocoptes gracilis                                                                        Dryberry mite                                                  Phyllocoptruta oleivora                                                                      Citrus rust mite                                               Phytoptus ribis                                                               Trisetacus pini                                                               Vasates amygdalina                                                            Vasates eurynotus                                                             Vasates quadripedes                                                                          Maple balddergall mite                                         Vasates schlechtendali                                            EUPODIDAE                                                                                 Penthaleus major                                                                             Winter grain mite                                              Linopodes spp.                                                    NALEPELLIDAE                                                                              Phylocoptella avellanae                                                                      Filbert bud mite                                   PENTHALEIDAE                                                                              Halotydeus destrustor                                             PYEMOTIDAE                                                                                Pyemotes tritici                                                                             Straw itch mite                                                Siteroptes cerealium                                              TARSONEMIDAE                                                                              Polyphagotarsonemus latus                                                                    Broad mite                                                     Steneotarsonemus pallidus                                                                    Cyclamen mite                                      TENUIPALPIDAE                                                                             Brevipalpus californicus                                                      Brevipalpus obovatus                                                                         Privet mite                                                    Brevipalpus lewisi                                                                           Citrus flat mite                                               Dolichotetranychus floridanus                                                                Pineapple flase spider                                                        mite                                                           Tenuipalpes granati                                                           Tenuipalpes pacificus                                             TETRANYCHIDAE                                                                             Bryobia arborea                                                               Bryobia practiosa                                                                            Clover mite                                                    Bryobia rubrioculus                                                                          Brown mite                                                     Eotetranychus coryli                                                          Eotetranychus hicoriae                                                                       Pecan deaf scorch mite                                         Eotetranychus lewisi                                                          Eotetranychus sexmaculatus                                                                   Sixspotted spider mite                                         Eotetranychus willametti                                                      Eotetranychus banksi                                                                         Texas citrus mite                                              Oligonychus ilicis                                                                           Southern red mite                                              Oligonychus pratensis                                                                        Banks grass mite                                               Oligonychus ununguis                                                                         Spruce spider mite                                             Panonychus citri                                                                             Citrus red mite                                                Panonychus ulmi                                                                              European red mite                                              Paratetranychus modestus                                                      Paratetranychus pratensis                                                     Paratetranychus viridis                                                       Petrobia latens                                                                              Brown wheat mite                                               Schizotetranychus celarius Bamboo spider mite                                  Schizotetranychus pratensis                                                  Tetranychus canadensis                                                                       Fourspotted spider mite                                        Tetranychus cinnabarinus                                                                     Carmine spider mite                                            Tetranychus mcdanieli                                                                        McDaniel spider mite                                           Tetranychus pacificus                                                                        Pacific spider mite                                            Tetranychus schoenei                                                                         Schoene spider mite                                            Tetranychus urticae                                                                          Twospotted spider mite                                         Tetranychus turkestani                                                                       Strawberry spider mite                                         Tetranychus desertorum                                                                       Desert spider mite                                 __________________________________________________________________________

The compounds are useful for reducing populations of insects and mites,and are used in a method of inhibiting an insect or mite populationwhich comprises applying to a locus of the insect or arachnid aneffective insect- or mite-inactivating amount of a compound of formula(1). The "locus" of insects or mites is a term used herein to refer tothe environment in which the insects or mites live or where their eggsare present, including the air surrounding them, the food they eat, orobjects which they contact. For example, plant-ingesting insects ormites can be controlled by applying the active compound to plant parts,which the insects or mites eat, particularly the foliage. It iscontemplated that the compounds might also be useful to protecttextiles, paper, stored grain, or seeds by applying an active compoundto such substance. The term "inhibiting an insect or mite" refers to adecrease in the numbers of living insects or mites; or a decrease in thenumber of viable insect or mite eggs. The extent of reductionaccomplished by a compound depends, of course, upon the application rateof the compound, the particular compound used, and the target insect ormite species. At least an insectinactivating or mite-inactivating amountshould be used. The terms "insect-inactivating amount" and"miteinactivating amount" are used to describe the amount, which issufficient to cause a measurable reduction in the treated insect or mitepopulation. Generally an amount in the range from about 1 to about 1000ppm active compound is used.

In a preferred embodiment, the present invention is directed to a methodfor inhibiting a mite which comprises applying to a plant an effectivemiteinactivating amount of a compound of formula (1) in accordance withthe present invention.

MITE/INSECT SCREEN

The compounds of Examples 1-295 were tested for miticidal andinsecticidal activity in the following mite/ insect screen.

Each test compound was formulated by dissolving the compound inacetone/alcohol (50:50) mixture containing 23 g of "TOXIMUL R"(sulfonate/nonionic emulsifier blend) and 13 g of "TOXIMUL S"(sulfonate/nonionic emulsifier blend) per liter. These mixtures werethen diluted with water to give the indicated concentrations.

Twospotted spider mites (Tetranychus urticae Koch) and melon aphids(Aphis gossypii Glover) were introduced on squash cotyledons and allowedto establish on both leaf surfaces. Other plants in the same treatmentpot were left uninfested. The leaves were then sprayed with 5 ml of testsolution using a DeVilbiss atomizing sprayer at 10 psi. Both surfaces ofthe leaves were covered until runoff, and then allowed to dry for onehour. Two uninfested leaves were then excised and placed into a Petridish containing southern armyworm (Spodopetra eridania Cramer).

After standard exposure periods, percent mortality was evaluated.Results are reported in Table 17, where the following abbreviations areused.

CRW refers to corn rootworm

SAW refers to Southern armyworm

SM refers to twospotted spider mites

MA refers to melon aphids.

                                      TABLE 17                                    __________________________________________________________________________    MITE/INSECT SCREEN                                                                    CRW CRW   SAW    SAW   SM    MA                                       COMPOUND                                                                              RATE                                                                              RESULTS                                                                             SM & MA                                                                              RESULTS                                                                             RESULTS                                                                             RESULTS                                  EX. NO. PPM %     RATE PPM                                                                             %     %     %                                        __________________________________________________________________________    1       12.00                                                                             0     200    0     0     0                                        2       12.00                                                                             0     200    0     0     0                                        3       12.00                                                                             0     200    0     0     0                                        4       12.00                                                                             0     200    0     0     0                                        5       12.00                                                                             0     200    0     0     0                                        6       12.00                                                                             0     200    0     0     0                                        7       12.00                                                                             0     200    0     0     0                                        8       12.00                                                                             0     200    100   0     0                                        9       12.00                                                                             0     200    0     0     0                                        10      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        11      24.00                                                                             60    400    100   0     0                                                12.00                                                                             0     200    80    0     0                                        12      24.00                                                                             40    400    100   0     0                                                12.00                                                                             0     200    0     0     0                                        13      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        14      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        15      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        16      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        17      12.00                                                                             0     200    0     0     0                                        18      12.00                                                                             0     200    0     0     0                                        19      12.00                                                                             0     200    0     0     0                                        20      12.00                                                                             0     200    0     0     0                                        21      12.00                                                                             0     200    0     0     0                                        22      12.00                                                                             0     200    0     0     0                                        23      12.00                                                                             0     200    0     0     0                                        24      12.00                                                                             0     200    0     0     0                                        25      12.00                                                                             0     200    0     0     0                                        26      12.00                                                                             0     200    0     0     0                                        27      12.00                                                                             0     200    0     0     0                                        28      12.00                                                                             0     200    0     0     0                                        29      12.00                                                                             0     200    0     0     0                                        30      12.00                                                                             0     200    0     0     0                                        31      12.00                                                                             0     200    0     0     0                                        32      12.00                                                                             0     200    0     0     0                                        33      12.00                                                                             0     200    0     0     0                                        34      12.00                                                                             0     200    0     0     0                                        35      12.00                                                                             0     200    0     0     0                                        36      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                                24.00                                                                             0     400    0     0     0                                        37      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        38      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        39      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        40      24.00                                                                             100   400    80    0     0                                                12.00                                                                             0     200    0     0     0                                        41      24.00                                                                             0     400    40    0     0                                                12.00                                                                             0     200    80    0     0                                        42      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        43      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        44      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        45      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        46      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        47      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        48      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        49      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        50      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        51      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    20    0     0                                        52      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        53      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        54      12.00                                                                             0     200    0     0     0                                        55      12.00                                                                             0     200    0     0     0                                        56      24.00                                                                             0     400    80    0     0                                                12.00                                                                             0     200    100   0     0                                        57      12.00                                                                             0     200    40    0     0                                                24.00                                                                             0     400    50    0     0                                        58      24.00                                                                             0     400    0     0     0                                        59      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        60      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        61      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        62      24.00                                                                             0     400    0     0     0                                        63      24.00                                                                             0     400    0     0     0                                        64      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    60    0     0                                        65      12.00                                                                             0     200    0     0     0                                        66      12.00                                                                             0     200    0     0     0                                        67      12.00                                                                             0     200    0     0     0                                        68      12.00                                                                             0     200    0     0     0                                        69      12.00                                                                             0     200    0     0     0                                        70      12.00                                                                             0     200    0     0     0                                        71      12.00                                                                             0     200    0     0     0                                                12.00                                                                             60    200    0     0     0                                        72      24.00                                                                             0     400    0     0     0                                        73      12.00                                                                             0     200    0     0     0                                        74      12.00                                                                             0     200    20    0     0                                                12.00                                                                             0     200    0     0     0                                        75      12.00                                                                             0     200    0     0     0                                        76      12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    90    0     0                                        77      12.00                                                                             0     200    0     0     0                                        78      12.00                                                                             0     200    20    0     0                                                12.00                                                                             0     200    20    0     0                                        79      12.00                                                                             0     200    10    0     0                                                12.00                                                                             0     200    60    0     0                                        80      12.00                                                                             0     200    0     0     0                                        81      12.00                                                                             0     200    0     0     0                                        82      12.00                                                                             0     200    0     0     0                                        83      12.00                                                                             0     200    0     0     0                                        84      12.00                                                                             0     200    10    0     0                                                24.00                                                                             0     400    0     0     0                                        85      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        86      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        87      12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        88      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        89      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        90      24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    100   80    80                                       91      12.00                                                                             0     200    0     0     0                                        92      12.00                                                                             0     200    0     0     0                                        93      12.00                                                                             0     200    0     0     0                                        94      12.00                                                                             100   200    0     0     0                                        95      12.00                                                                             0     200    20    0     0                                                12.00                                                                             0     200    40    0     0                                        96      12.00                                                                             0     200    100   0     0                                                12.00                                                                             0     200    100   0     0                                        97      12.00                                                                             0     200    0     0     0                                        98      12.00                                                                             0     200    0     0     0                                        99      12.00                                                                             0     200    0     0     0                                        100     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        101     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        102     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    50    0     0                                        103     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        104     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    60    0     0                                        105     12.00                                                                             0     200    30    100   80                                               24.00                                                                             0     400    0     0     50                                       106     24.00                                                                             0     400    0     0     0                                        107     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        108     12.00                                                                             0     200    0     0     0                                        109     24.00                                                                             0     400    0     0     0                                        110     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        111     12.00                                                                             0     200    20    90    0                                                24.00                                                                             0     400    20    80    0                                        112     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        113     12.00                                                                             0     200    100   40    0                                                24.00                                                                             100   400    70    0     0                                        114     24.00                                                                             0     400    70    100   30                                       115     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        116     12.00                                                                             0     200    0     0     0                                        117     12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    0     0     0                                        118     12.00                                                                             0     200    0     0     0                                        119     12.00                                                                             0     200    0     0     0                                        120     12.00                                                                             0     200    0     0     0                                        121     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        122     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        123     12.00                                                                             0     200    0     0     0                                        124     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        125     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        126     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        127     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        128     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        129     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        130     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        131     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        132     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        133     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        134     24.00                                                                             0     400    0     0     0                                        135     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        136     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        137     24.00                                                                             0     400    100   80    80                                       138     24.00                                                                             0     400    0     0     0                                        139     12.00                                                                             0     200    0     0     0                                        140     24.00                                                                             0     400    60    0     0                                                12.00                                                                             0     200    0     0     0                                        141     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        142     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        143     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        144     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        145     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        146     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        147     12.00                                                                             0     200    0     0     0                                        148     12.00                                                                             0     200    0     0     0                                        149     12.00                                                                             0     200    0     0     0                                        150     12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    0     0     0                                        151     12.00                                                                             0     200    0     0     0                                        152     12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    0     0     0                                        153     12.00                                                                             0     200    0     0     0                                        154     12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    0     0     0                                        155     12.00                                                                             0     200    0     0     0                                        156     12.00                                                                             0     200    0     0     0                                                12.00                                                                             0     200    0     0     0                                        157     24.00                                                                             0     400    100   80    0                                        158     12.00                                                                             0     200    0     0     0                                        159     12.00                                                                             0     200    0     0     0                                        160     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        161     24.00                                                                             40    400    0     0     80                                               12.00                                                                             0     200    0     0     0                                        162     12.00                                                                             0     200    0     0     0                                        163     12.00                                                                             0     200    0     0     0                                        164     12.00                                                                             0     200    0     0     0                                        165     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        166     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        167     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        168     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        169     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        170     12.00                                                                             0     200    0     0     0                                        171     12.00                                                                             0     200    0     0     0                                        172     12.00                                                                             0     200    0     0     0                                        173     12.00                                                                             0     200    0     0     0                                        174     12.00                                                                             0     200    0     0     0                                        175     12.00                                                                             0     200    0     0     0                                        176     12.00                                                                             0     200    0     0     0                                        177     12.00                                                                             0     200    0     0     0                                                24.00                                                                             100   400    0     0     0                                        178     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        179     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        180     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        181     12.00                                                                             0     200    0     0     0                                        182     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        183     12.00                                                                             0     200    0     0     0                                        184     12.00                                                                             0     200    0     0     0                                        185     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        186     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        187     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        188     24.00                                                                             0     400    0     0     0                                        189     12.00                                                                             0     200    0     0     0                                        190     12.00                                                                             0     200    0     0     0                                        191     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        192     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        193     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        194     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        195     24.00                                                                             0     400    0     0     0                                        196     24.00                                                                             0     400    0     100   100                                      197     24.00                                                                             0     400    80    90    80                                       198     24.00                                                                             0     400    0     90    80                                       199     24.00                                                                             100   400    0     0     0                                        200     24.00                                                                             0     400    50    100   100                                              12.00                                                                             0     200    0     100   100                                      201     12.00                                                                             0     200    0     80    100                                              24.00                                                                             0     400    0     80    100                                      202     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        203     12.00                                                                             0     200    10    0     100                                              24.00                                                                             0     400    0     0     90                                       204     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    100   0     50                                       205     24.00                                                                             0     400    0     0     0                                        206     24.00                                                                             0     400    0     0     0                                        207     12.00                                                                             0     200    0     0     0                                        208     12.00                                                                             0     200    0     10    10                                       209     12.00                                                                             0     200    10    0     0                                                12.00                                                                             0     200    100   0     40                                       210     12.00                                                                             0     200    0     0     0                                        211     12.00                                                                             0     200    0     10    40                                       212     12.00                                                                             0     200    0     0     0                                        213     12.00                                                                             0     200    0     0     0                                        214     24.00                                                                             0     400    0     0     0                                        215     24.00                                                                             0     400    0     100   100                                      216     24.00                                                                             100   400    0     0     0                                        217     24.00                                                                             0     400    0     0     0                                        218     24.00                                                                             0     400    100   0     0                                        219     12.00                                                                             0     200    0     0     0                                        220     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        221     24.00                                                                             0     400    0     90    80                                               12.00                                                                             40    200    0     90    90                                       222     24.00                                                                             0     400    0     0     40                                               12.00                                                                             0     200    0     0     50                                       223     24.00                                                                             0     400    0     0     100                                              12.00                                                                             80    200    0     0     80                                       224     24.00                                                                             0     400    0     0     0                                        225     24.00                                                                             0     400    0     0     0                                        226     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        227     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        228     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     80                                       229     12.00                                                                             0     200    0     50    50                                               24.00                                                                             0     400    0     0     0                                        230     12.00                                                                             0     200    0     100   90                                               24.00                                                                             0     400    0     80    0                                        231     12.00                                                                             0     200    0     90    0                                                24.00                                                                             0     400    0     40    50                                       232     24.00                                                                             0     400    30    80    40                                               12.00                                                                             0     200    0     100   70                                       233     12.00                                                                             0     200    0     100   50                                               24.00                                                                             0     400    0     80    80                                       234     12.00                                                                             0     200    60    50    50                                               24.00                                                                             0     400    0     30    100                                      235     24.00                                                                             0     400    0     0     50                                               12.00                                                                             0     200    80    0     0                                        236     24.00                                                                             40    400    0     0     30                                               12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        237     24.00                                                                             0     400    0     100   0                                                12.00                                                                             0     200    0     0     0                                        238     24.00                                                                             0     400    100   0     0                                                12.00                                                                             0     200    0     100   100                                      239     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        240     24.00                                                                             0     400    0     0     0                                        241     24.00                                                                             0     400    0     0     0                                        242     24.00                                                                             0     400    0     0     0                                                12.00                                                                             0     200    0     0     0                                        243     24.00                                                                             0     400    0     0     0                                        244     12.00                                                                             0     200    0     0     40                                       245     12.00                                                                             0     200    0     0     0                                        246     12.00                                                                             0     200    0     0     0                                        247     24.00                                                                             0     400    50    0     0                                                12.00                                                                             0     200    20    90    0                                        248     24.00                                                                             0     400    0     0     0                                        249     24.00                                                                             0     400    0     0     0                                        250     24.00                                                                             0     400    0     0     0                                        251     12.00                                                                             0     200    0     0     0                                        252     24.00                                                                             0     400    0     90    100                                              12.00                                                                             0     200    0     90    100                                      253     24.00                                                                             0     400    0     100   100                                              12.00                                                                             0     200    0     100   90                                       254     24.00                                                                             0     400    0     0     0                                        255     24.00                                                                             0     400    0     0     0                                        256     24.00                                                                             100   400    100   0     0                                        257     24.00                                                                             0     400    0     0     0                                        258     24.00                                                                             0     400    0     90    100                                      259     24.00                                                                             0     400    0     80    80                                               12.00                                                                             0     200    0     100   90                                       260     24.00                                                                             40    400    40    0     0                                                12.00                                                                             0     200    100   100   100                                      261     24.00                                                                             100   400    80    50    100                                              12.00                                                                             0     200    100   90    100                                      262     12.00                                                                             0     200    0     100   100                                              24.00                                                                             0     400    0     100   100                                      263     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        264     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        265     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        266     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        267     12.00                                                                             0     200    0     40    20                                               24.00                                                                             0     400    0     100   100                                      268     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     80    0                                        269     12.00                                                                             0     200    0           30                                               24.00                                                                             40    400    0     0     0                                        270     12.00                                                                             0     200    20    0     0                                                24.00                                                                             0     400    0     80    0                                        271     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        272     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     20    0                                        273     24.00                                                                             0     400    0     0     0                                        274     12.00                                                                             0     200    0     100   100                                              24.00                                                                             0     400    0     0     100                                      275     12.00                                                                             0     200    0     0     90                                               24.00                                                                             0     400    0     60    100                                      276     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     60    80                                       277     24.00                                                                             0     400    0     0     0                                        278     12.00                                                                             0     200    0     60    90                                               24.00                                                                             0     400    100   0     0                                        279     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     80                                       280     12.00                                                                             0     200    60    0     0                                                24.00                                                                             0     400    0     0     0                                        281     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        282     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        283     12.00                                                                             0     200    0     0     80                                               24.00                                                                             0     400    0     80    0                                        284     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        285     12.00                                                                             0     200    0     40    80                                               24.00                                                                             0     400    0     0     0                                        286     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        287     12.00                                                                             0     200    0     0     80                                               24.00                                                                             0     400    0     0     0                                        288     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        289     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        290     12.00                                                                             0     200    0     80    80                                               24.00                                                                             0     400    0     0     0                                        291     12.00                                                                             0     200    0     0     100                                              24.00                                                                             0     400    0     0     0                                        292     12.00                                                                             0     200    0     0     30                                               24.00                                                                             0     400    0     0     0                                        293     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        294     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        295     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        296     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     80                                       297     12.00                                                                             0     200    100   100   100                                              24.00                                                                             0     400    100   100   100                                      298     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        299     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        300     12.00                                                                             0     200    20    0     0                                                24.00                                                                             0     400    0     0     0                                        301     12.00                                                                             0     200    40    0     0                                                24.00                                                                             0     400    0     0     0                                        302     12.00                                                                             0     200    100   100   100                                              24.00                                                                             0     400    0     0     100                                      303     12.00                                                                             0     200    0     100   100                                              24.00                                                                             0     400    0     0     100                                      304     12.00                                                                             0     200    0     100   100                                              24.00                                                                             0     400    0     100   80                                       305     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        306     12.00                                                                             0     200    0     100   100                                              24.00                                                                             100   400    100   0     0                                        307     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        308     12.00                                                                             0     200    0     0     80                                               24.00                                                                             0     400    0     0     80                                       309     12.00                                                                             0     200    0     40    60                                               24.00                                                                             0     400    100   0     0                                        310     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     90                                       311     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     40                                       312     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        313     12.00     200                                                                 24.00                                                                             0     400    0     30    0                                        314     24.00                                                                             100   400    0     100   100                                      317     12.00                                                                             0     200    80    80    80                                               24.00                                                                             0     400    0     0     60                                       318     12.00     200                                                                 24.00                                                                             0     400    0     0     0                                        319     12.00     200                                                                 24.00                                                                             0     400    0     100   100                                      320     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        321     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        322     12.00                                                                             0     200    60    100   80                                               24.00                                                                             0     400    60    80    100                                      323     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        324     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        325     12.00                                                                             0     200    0     0     80                                               24.00                                                                             0     400    80    0     0                                        326     12.00                                                                             0     200    0     0     0                                                24.00                                                                             0     400    0     0     0                                        327     12.00                                                                             0     200    80    0     100                                              24.00                                                                             60    400    0     80    60                                       328     12.00                                                                             100   200    100   80    80                                               24.00                                                                             100   400    100   0     0                                        __________________________________________________________________________

Field Trials

4-[2-[4-(t-Butyl)phenyl]ethoxy]-8-fluoroquinoline (Example 221) wasevaluated in a number of field trials. The following table reports thehost plants on which it was tested and the pest species against which itshowed activity.

                  TABLE 18                                                        ______________________________________                                        HOST            PEST                                                          ______________________________________                                        alfalfa (Lucerne)                                                                             pea aphid, potato leaf hopper,                                                tarnished plant bug, green                                                    cloverworm                                                    apples          mites, apple aphid, European red                                              mite, green peach aphid, white                                                apple leafhopper, apple rust mite,                                            rosy apple aphid                                              azaleas         greenhouse thrip                                              bean, faba broad                                                                              bean aphid                                                    broccoli        twospotted spider mite                                        cotton          cotton aphid                                                  grape (European)                                                                              grape thrip, grape leafhopper                                 hops            Dawson-hop aphid                                              pea, garden (English)                                                                         pea aphid                                                     pecan nut       yellow hickory aphid                                          privet          thrip                                                         sugar beet      green peach aphid                                             wheat           wheat aphid                                                   ______________________________________                                    

Compositions

The compounds of this invention are applied in the form of compositionswhich are important embodiments of the invention, and which comprise acompound of this invention and a phytologically-acceptable inertcarrier. The compositions are either concentrated formulations which aredispersed in water for application, or are dust or granular formulationswhich are applied without further treatment. The compositions areprepared according to procedures and formulae which are conventional inthe agricultural chemical art, but which are novel and important becauseof the presence therein of the compounds of this invention. Somedescription of the formulation of the compositions will be given,however, to assure that agricultural chemists can readily prepare anydesired composition.

The dispersions in which the compounds are applied are most oftenaqueous suspensions or emulsions prepared from concentrated formulationsof the compounds. Such water-soluble, water-suspendable or emulsifiableformulations are either solids usually known as wettable powders, orliquids usually known as emulsifiable concentrates or aqueoussuspensions. Wettable powders, which may be compacted to form waterdispersible granules, comprise an intimate mixture of the activecompound, an inert carrier and surfactants. The concentration of theactive compound is usually from about 10% to about 90% by weight. Theinert carrier is usually chosen from among the attapulgite clays, themontmorillonite clays, the diatomaceous earths, or the purifiedsilicates. Effective surfactants, comprising from about 0.5% to about10% of the wettable powder, are found among the sulfonated lignins, thecondensed naphthalenesulfonates, the naphthalenesulfonates, thealkylbenzenesulfonates, the alkyl sulfates, and nonionic surfactantssuch as ethylene oxide adducts of alkyl phenols.

Emulsifiable concentrates of the compounds comprise a convenientconcentration of a compound, such as from about 50 to about 500 gramsper liter of liquid, equivalent to about 10% to about 50%, dissolved inan inert carrier which is either a water miscible solvent or a mixtureof water-immiscible organic solvent and emulsifiers. Useful organicsolvents include aromatics, especially the xylenes, and the petroleumfractions, especially the high-boiling naphthalenic and olefinicportions of petroleum such as heavy aromatic naphtha. Other organicsolvents may also be used, such as the terpenic solvents including rosinderivatives, aliphatic ketones such as cyclohexanone, and complexalcohols such as 2-ethoxyethanol. Suitable emulsifiers for emulsifiableconcentrates are chosen from conventional nonionic surfactants, such asthose mentioned above.

Aqueous suspensions comprise suspensions of water-insoluble compounds ofthis invention, dispersed in an aqueous vehicle at a concentration inthe range from about 5% to about 50% by weight. Suspensions are preparedby finely grinding the compound, and vigorously mixing it into a vehiclecomprised of water and surfactants chosen from the same types discussedabove. Inert ingredients, such as inorganic salts and synthetic ornatural gums, may also be added, to increase the density and viscosityof the aqueous vehicle. It is often most effective to grind and mix thecompound at the same time by preparing the aqueous mixture, andhomogenizing it in an implement such as a sand mill, ball mill, orpistontype homogenizer.

The compounds may also be applied as granular compositions, which areparticularly useful for applications to the soil. Granular compositionsusually contain from about 0.5% to about 10% by weight of the compound,dispersed in an inert carrier which consists entirely or in large partof clay or a similar inexpensive substance. Such compositions areusually prepared by dissolving the compound in a suitable solvent, andapplying it to a granular carrier which has been pre-formed to theappropriate particle size, in the range of from about 0.5 to 3 mm. Suchcompositions may also be formulated by making a dough or paste of thecarrier and compound, and crushing and drying to obtain the desiredgranular particle size.

Dusts containing the compounds are prepared simply by intimately mixingthe compound in powdered form with a suitable dusty agriculturalcarrier, such as kaolin clay, ground volcanic rock and the like. Dustscan suitably contain from about 1% to about 10% of the compound.

It is equally practical, when desirable for any reason, to apply thecompound in the form of a solution in an appropriate organic solvent,usually a bland petroleum oil, such as the spray oils, which are widelyused in agricultural chemistry.

Insecticides and miticides are generally applied in the form of adispersion of the active ingredient in a liquid carrier. It isconventional to refer to application rates in terms of the concentrationof active ingredient in the carrier. The most widely used carrier iswater.

The compounds of the invention can also be applied in the form of anaerosol composition. In such compositions the active compound isdissolved or dispersed in an inert carrier, which is apressure-generating propellant mixture. The aerosol composition ispackaged in a container from which the mixture is dispensed through anatomizing valve. Propellant mixtures comprise either low-boilinghalocarbons, which may be mixed with organic solvents, or aqueoussuspensions pressurized with inert gases or gaseous hydrocarbons.

The actual amount of compound to be applied to loci of insects and mitesis not critical and can readily be determined by those skilled in theart in view of the examples above. In general, concentrations of from 10ppm to 5000 ppm of compound are expected to provide good control. Withmany of the compounds, concentrations of from 100 to 1500 ppm willsuffice. For field crops, such as soybeans and cotton, a suitableapplication rate for the compounds is about 0.5 to 1.5 lb/A, typicallyapplied in 50 gal/A of spray formulation containing 1200 to 3600 ppm ofcompound. For citrus crops, a suitable application rate is from about100 to 1500 gal/A spray formulation, which is a rate of 100 to 1000 ppm.

The locus to which a compound is applied can be any locus inhabited byan insect or arachnid, for example, vegetable crops, fruit and nuttrees, grape vines, and ornamental plants. Inasmuch as many mite speciesare specific to a particular host, the foregoing list of mite speciesprovides exemplification of the wide range of settings in which thepresent compounds can be used.

Because of the unique ability of mite eggs to resist toxicant action,repeated applications may be desirable to control newly emerged larvae,as is true of other known acaricides.

The following formulations of compounds of the invention have beenprepared, and are typical of compositions useful in the practice of thepresent invention.

    ______________________________________                                        A. Aqueous Suspension                                                         ______________________________________                                        8-Fluoro-N-[2-(2-naphthyl)ethyl]-4-quinolinamine                                                          12.5%                                             "TERGITOL TMN-6" (nonionic surfactant)                                                                    1.0%                                              "ZEOSYL 200" (silica)       1.0%                                              "AF-100" (silicon based antifoam agent)                                                                   0.2%                                              2% xanthan solution         10.0%                                             "MAKON 10" (10 moles ethyleneoxide nonylphenol                                                            9.0%                                              surfactant)                                                                   tap water                   66.3%                                             ______________________________________                                    

    ______________________________________                                        B. Emulsifiable Concentrate                                                   ______________________________________                                        4[-2-[4-( .sub.- t-Butyl)phenyl]ethoxy]-8-fluoroquinoline                                                12.4%                                              "EXXON 200" (naphthalene solvent)                                                                        83.6%                                              "TOXIMUL H" (nonionic/anionic surfactant blend)                                                          2.0%                                               "TOXIMUL D" (nonionic/anionic surfactant blend)                                                          2.0%                                               ______________________________________                                    

We claim:
 1. A fungicidal method which comprises applying to the locusof a plant pathogen a fungicidally effective but non-pytotoxic amount ofa compound of the formula (1) ##STR11## wherein: R¹ to R⁴ areindependentlyH, halo, (C₁ -C₄) alkyl, branched (C₃ -C₄) alkyl, halo (C₁-C₄) alkyl, (C₁ -C₄) alkoxy, NO₂, or NH₂, at least two of R¹ to R⁴ beingH, or one of R² to R⁴ is --NR⁷ --Y--Ar or O--Y--AR and the rest of R¹ toR⁴ are H; W is N, or CR⁵ ; R⁵ is H, CH₃, Cl, O--Y--Ar, or --NR⁷ --Y--Ar;R⁶ is H, CH₃, Cl, or Br; A is --O--Alk or --X--Y--Ar; Alk is a C₂ -C₁₈saturated or unsaturated hydrocarbon chain, straight chain or branched,optionally substituted with halo, halo (C₁ -C₄) alkoxy, (C₃ -C₈)cycloalkyl, hydroxy, or acetyl; X is O, NR⁷, or CR⁸ R⁹, provided that ifone of R² to R⁵ is NR⁷ --Y--AR or O--Y--Ar, then X--Y--Ar is anidentical group; R⁷ is H, (C₁ -C₄) alkyl, or acetyl; R⁸ and R⁹ areindependently H, (C₁ -C₄) alkyl, halo, or OH, or R⁸ and R⁹ combine toform a saturated or unsaturated carbocyclic ring comprising three toseven carbon atoms; Y is an alkylene chain 2 to 8 carbon atoms long thatoptionally includes an O, S, SO, SO₂, or NR⁷ group, and optionallyincludes a saturated or unsaturated carbocyclic ring comprising three toseven carbon atoms, and optionally is substituted with (C₁ -C₃) alkyl,(C₂ -C₄) alkenyl, phenyl, (C₃ -C₈) cycloalkyl, hydroxy, halo, or acety;and Ar is
 1. 3-benzodioxolylfluorenyl, pyridyl, substituted pyridyl,indolyl, furanyl, substituted furanyl, thienyl, optionally substitutedwith CH₃ or Cl, thiazolyl, cyclopentyl, 1-methylcyclopentyl,cyclohexenyl (tetrahydrophenyl), cyclohexyl (hexahydrophenyl), naphthyl,substituted naphthyl, dihydronaphthyl, tetrahydronaphthyl,decahydronaphthyl, or a group of formula (2); ##STR12## where R¹⁰ to R¹⁴are independently H, halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl,halo (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy,substituted phenoxy, phenylthio, substituted phenylthio, phenyl,substituted phenyl, NO₂, NH₂, acetoxy, OH, CN, SiR¹⁵ R¹⁶ R¹⁷, or OSiR¹⁵R¹⁶ R¹⁷, where R¹⁵, R¹⁶, and R¹⁷ are independently (C₁ -C₄) alkyl or (C₃-C₄) branched alkyl, phenyl, or substituted pehnyl, provided that unlesseach of R¹⁰ to R¹⁴ is F, CH₃, or H, then at least two of R¹⁰ to R¹⁴ areH: or an acid addition salt of a compound of formula (1) or an N-oxideof a compound of formula (1) when W is CR⁵ ; where, in the foregoingdefinitions, the term substituted phenyl refers to phenyl substitutedwith up to three groups selected from halo, (C₁ -C₁₀) alkyl, branched(C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy (C₁ -C₇) alkyl, (C₁ -C₇)alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN, (C₁ -C₄)alkanoyloxy, or benzyloxy; the term substituted phenoxy refers to aphenoxy group substituted with up to three groups selected from halo,(C₁ ∝C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, hydroxy(C₁ -C₇)alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy, phenyl,NO₂, OH, CN (C₁ -C₄) alkanoyloxy, or benzyloxy; the term substitutedphenylthio refers to a phenylthio group substituted with up to threegroups selected from halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl,halo (C₁ -C₇) alkoxy, phenoxy, phenyl, NO₂, OH, CN (C₁ -C₄) alkanoyloxy,or benzyloxy; the term substituted phenylsulfonyl refers to aphenylsulfonyl group substituted with up to three groups selected fromhalo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl,hydroxy (C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy,phenyl, NO₂, OH, CN (C₁ -C₄) alkanoyloxy, or benzyloxy; and the termssubstituted naphthyl, substituted pyridyl, and substituted furanyl referto these ring systems substituted with halo, halo (C₁ -C₄) alkyl, CN,NO₂, (C₁ -C₄) alkyl, (C₃ -C₄) branched alkyl, phenyl, (C₁ -C₄) alkoxy,or halo (C₁ -C₄) alkoxy.
 2. A method of claim 1 wherein the compound offormula (1) is one whereinA is --X--Y--Ar; R⁸ and R⁹ are independently Hor (C₁ -C₄) alkyl, or R⁸ and R⁹ combine to form a saturated orunsaturated carbocyclic ring comprising three to seven carbon atoms; Yis an alkylene chain 2 to 6 carbon atoms long, optionally including asaturated or unsaturated carbocyclic ring comprising three to sevencarbon atoms, or substituted with (C₁ -C₃) alkyl, phenyl, (C₃ -C₈)cycloalkyl, hydroxy, halo, or acetyl; and Ar is 1,3-benzodioxolylfluorenyl,pyridyl, indolyl, thienyl, optionally substituted with CH₃ orCl, thiazolyl, cyclohexenyl (tetrahydrophenyl), cyclohexyl(hexahydrophenyl), naphthyl, dihydronaphthyl, tetrahydronaphthyl,decahydronaphthyl, or a group of formula (2); ##STR13## R¹⁰ to R¹⁴ areindependently H, halo, (C₁ -C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo(C₁ -C₇) alkyl, (C₁ -C₇) alkoxy, halo (C₁ -C₇) alkoxy, phenoxy,substituted phenoxy, phenylthio, substituted phenylthio, phenyl,substituted pehnyl, NO₂, OH, or CN, provided that unless each of R¹⁰ toR¹⁴ is F, CH₃, or H, then at least two of R¹⁰ to R¹⁴ are H.
 3. A methodof claim 1 wherein the compound of formula (1) is one wherein W is CH.4. A method of claim 1 wherein the compound of formula (1) is onewherein R⁶ is H.
 5. A method of claim 1 wherein the compound of formula(1) is one wherein at least three of R¹ to R⁴ are H.
 6. A method ofclaim 1 wherein the compound of formula (1) is one wherein R³ is Cl orF.
 7. A method of claim 1 wherein the compound of formula (1) is onewherein R⁴ is F.
 8. A method of claim 1 wherein the compound of formula(1) is one wherein A is X--Y--Ar.
 9. A method of claim 1 wherein thecompound of formula (1) is one wherein A is --O--(CH₂)₂ --Ar.
 10. Amethod of claim 1 wherein the compound of formula (1) is one wherein Ais --NR⁷ --(CH₂)₂ --Ar.
 11. A method of claim 1 wherein the compound offormula (1) is one wherein A is --CR⁸ R⁹ --(CH₂)₂ --Ar.
 12. A method ofclaim 1 wherein the compound of formula (1) is one wherein Ar isnaphthyl.
 13. A method of claim 1 wherein the compound of formula (1) isone wherein Ar is thienyl.
 14. A method of claim 1 wherein the compoundof formula (1) is one wherein Ar is thiazolyl.
 15. A method of claim 1wherein the compound of formula (1) is one wherein Ar is cyclohexenyl.16. A method of claim 1 wherein the compound of formula (1) is onewherein Ar is an optionally substituted phenyl group of formula (2). 17.A method of claim 1 wherein the compound of formula (1) is one whereinWis CH; A is X--(CH₂)₂ --Ar; and Ar is a group of formula (2) ##STR14##wherein four of R¹⁰ to R¹⁴ are H and one of R¹⁰ to R¹⁴ is Cl, (C₁ -C₄)alkyl, halo (C₁ -C₇) alkyl, branched (C₃ -C₆) alkyl, (C₁ -C₇) alkoxy,halo (C₁ -C₇) alkoxy, phenyl, substituted phenyl, phenoxy, orsubstituted phenoxy.
 18. A method of claim 1 wherein the compound offormula (1) is one wherein R⁴ is F.
 19. A fungicidal method of claim 1wherein the compound of formula (1) is one wherein:W is CH; `A isX--Y--Ar; X is O; Y is an alkylene chain 2 to 8 carbon atoms long; Ar isa phenyl group of formula (2) wherein R¹⁰ to R¹⁴ are H, halo, I, (C₁-C₁₀) alkyl, branched (C₃ -C₆) alkyl, halo (C₁ -C₇) alkyl, (C₁ -C₇)alkoxy, halo (C₁ -C₇) alkoxy.
 20. A method of claim 17 wherein thecompound of Formula (1) is one wherein X is O.
 21. A method of claim 20wherein the compound of Formula (1) is one wherein R⁴ is F.
 22. A methodof claim 17 wherein the compound of Formula (1) is one wherein X is NH.23. A method of claim 17 wherein R⁴ is F.
 24. A method of claim 17wherein the compound of Formula (1) is one wherein X is CH₂.
 25. Amethod of claim 24 wherein R⁴ is F.
 26. A method of claim 21 wherein thecompound is selectedfrom:8-fluoro-4-(2-(3-trifluoromethyl)phenyl)ethoxy)quinoline;8-fluoro-4-(2-(4-methylphenyl)ethoxy)quinoline;4-(20(4-(t-butyl)phenyl)ethoxy-8-fluoroquinoline;8-fluoro-4-(2-(3-(trifluoromethyl)phenyl)ethoxy)quinoline;8-fluoro-4-(2-(4-methylphenyl)ethoxy)quinoline;8-fluoro-4(2-(2-(trifluoromethyl)phenyl)ethoxy)quinoline;4-(2-(4-chlorophenyl)ethoxy)-8-fluoroquinoline;8-fluoro-4-(2-(2-(trifluoromethyl)phenyl)ethoxy)quinoline;4-(2-(4-chlorophenyl)ethoxy)-8-fluoroquinoline;4-(2-(4-methylphenyl)ethoxy)quinoline;8-fluoro-4-(2-phenylethoxy)quinoline;8-fluoro-4-(2-phenylethoxy)quinoline;8-fluoro-4-(2-(3-methylphenyl)ethoxy)quinoline;8-fluoro-4-(2-(2-fluorophenyl)ethoxy)quinoline;8-fluoro-4-(2-(2-methoxyphenyl)ethoxy)quinoline;and 8-fluoro-4-(2-(2-methoxyphenyl)ethoxy)quinoline; and8-fluoro-N-(2-(1,1'-biphenyl)-4-yl-ethoxy)quinoline;4-(2-(3-chlorophenyl)ethoxy)-8-fluoroquinoline;8-fluoro-4-(2-(4-(i-propyl)phenyl)ethoxy)quinoline;8-fluoro-4(2-(3-(trifluoromethyl)phenylethoxy)quinoline;8-fluoro-4-(2-(4-methoxyphenyl)ethoxy)quinoline;8-fluoro-4-(2-(3-phenoxyphenyl)ethoxy)quinoline;8-fluoro-4-(2-(1,1'-biphenyl)-2-yl-ethoxy)quinoline.
 27. A method ofclaim 23 wherein the compound is selectedfrom:8-fluoro-N-(2-phenylethyl)-4-quinolinamine;8-fluoro-N-(2-(2-(trifluoromethyl)phenyl)ethyl)-4-quinolinamine;8-fluoro-N-(2-(3-(trifluoromethyl)phenyl)ethyl)-4-quinolinamine;N-(2-(4(b 1-methylethyl)phenyl)ethyl)-8-fluoro-4-quinolinamine;4-(2-(3-chlorophenyl)ethoxy)-8-fluoroquinoline;N-(2-(4-(i-propyl)-phenyl)ethyl)-8-fluoro-4-quinolinamine;8-fluoro-N-(2-(3-phenoxyphenyl)ethyl(-4-quinolinamine;N-(2-(4-(i-propyl)phenyl)ethyl)-8-fluoro-4-quinolinamine;N-(2-(1,1'-bi-henyl)-3-ylethyl)-8-fluoro-4quinolinamine;N-(2-(2,4-dichlorophenyl)ethyl)-8-fluoro-4-quinolinamine;8-fluoro-N-(2-(4-iodophenyl)ethyl)-4-quinoliamine;N-(2-(4-bromophenyl)ethyl)-8-fluoro-4-quinolinamine;N-(2-(4-chlorophenyl)ethyl)-8-fluoro-4-quinolinamine;N-(2-(4-chlorophenyl)ethyl)-N-ethyl-8-fluoro-4-quinolinamine;N-(3-(1,1'-biphenyl)-4-ylpropyl)-8-fluoro-4-quinolinamine;8-fluoro-N-(2-(4-phenoxyphenyl)ethyl)-4-quinolinamine;N-(2-(4-(t-butyl)phenyl)ethyl)-8-fluoro-4-quinolinamine;N-(2-(4-(i-propyl)phenyl)ethyl)-8-fluoro-4-quinolinamine.
 28. A methodof claim 25 wherein the compound is selectedfrom:8-fluoro-4-(3-(4-t-butyl)phenyl)propyl)quinoline;8-fluoro-4-(3-(4-(i-propyl)phenyl)propyl)quinoline;8-fluoro-4-(3-phenylpropyl)quinoline;8-fluoro-4-(3-(4-methylpheny)propyl)quinoline; and8-fluoro-4-(3-(3-(trifluoromethyl)phenyl)propyl)-quinoline.